Process for producing phosphonium borate compound, novel phosphonium borate compound, and method of using the same

Info

Patent number: 7728176
Type: Grant
Filed: Nov 26, 2004
Date of Patent: Jun 1, 2010
Patent Publication Number: 20070098616
Assignee: Hokko Chemical Industry Co., Ltd. (Tokyo)
Inventors: Shin Masaoka (Atsugi), Hideyuki Iwazaki (Atsugi)
Primary Examiner: Sikarl A Witherspoon
Assistant Examiner: Chukwuma O Nwaonicha
Attorney: The Webb Law Firm, P.C.
Application Number: 10/580,699

Abstract

The invention relates to a phosphonium borate compound represented by Formula (I) (hereinafter, the compound (I)). The invention has objects of providing (A) a novel process whereby the compound is produced safely on an industrial scale, by simple reaction operations and in a high yield; (B) a novel compound that is easily handled; and (C) novel use as catalyst. Formula (I): (R1)(R2)(R3)PH.BAr4 (I) wherein R1, R2, R3 and Ar are as defined in the specification. The process (A) includes reacting a phosphine with a) HCl or b) H2SO4 to produce a) a hydrochloride or b) a sulfate; and reacting the salt with a tetraarylborate compound. The compound (B) has for example a secondary or tertiary alkyl group as R1 and is easily handled in air without special attention. The use (C) is characterized in that the compound (I) is used instead of an unstable phosphine compound of a transition metal complex catalyst for catalyzing C—C bond, C—N bond and C—O bond forming reactions and the compound produces an effect that is equal to that achieved by the transition metal complex catalyst.

Description

Description

FIELD OF THE INVENTION

The present invention relates to a process for producing a phosphonium borate compound, a novel phosphonium borate compound, and use of the compound.

BACKGROUND OF THE INVENTION

Transition metal complexes having alkylphosphine compounds as ligands are very important catalysts in carbon-carbon bond forming reactions such as Suzuki-Miyaura reaction, carbon-nitrogen bond forming reactions such as Buchwald-Hartwig amination, and carbon-oxygen bond forming reactions such as ether synthesis (see Nonpatent Document 1). As an example, bis(tri-tert-butylphosphine)palladium (0) is used.

Many of the transition metal complexes having alkylphosphine ligands are very expensive, and the industrial availability thereof is low. Further, synthesis of the transition metal complexes having alkylphosphine ligands is difficult because the raw-material alkylphosphine compounds are generally extremely susceptible to air oxidation and possess combustibility.

For such reasons, the alkylphosphine compounds are used together with transition metals, salts thereof, oxides thereof or complexes thereof in the reaction system, in place of the isolated transition metal complexes having alkylphosphine ligands (see Nonpatent Documents 1 and 3). For example, di-tert-butylmethylphosphine, tri-tert-butylphosphine or tricyclohexylphosphine is used together with palladium (II) acetate or tris(dibenzylideneacetone)dipalladium (0) in the reaction system.

However, many of the alkylphosphine compounds are extremely susceptible to air oxidation and possess combustibility, and therefore are difficult to handle.

To improve the susceptibility to air oxidation, alkylphosphonium tetrafluoroborates, quaternary salts of alkylphosphines and boron compounds, have been studied. Examples of the alkylphosphonium tetrafluoroborates include:

(1) triethylphosphonium tetrafluoroborate (see Nonpatent Document 2);

(2) tricyclohexylphosphonium tetrafluoroborate (see Nonpatent Document 4);

(3) di-tert-butylmethylphosphonium tetrafluoroborate (see Nonpatent Document 3);

(4) tri-n-butylphosphonium tetrafluoroborate (see Nonpatent Document 5); and

(5) tri-tert-butylphosphonium tetrafluoroborate (see Nonpatent Document 4).

These compounds are produced from alkylphosphine compounds and fluoroboric acid (see Nonpatent Document 5).

As known in the art, the above compounds are used together with transition metals, salts thereof, oxides thereof or complexes thereof in the carbon-carbon bond forming reactions such as Suzuki-Miyaura reaction (see Nonpatent Documents 3 and 5). For example, di-tert-butylmethylphosphonium tetrafluoroborate or tri-tert-butylphosphonium tetrafluoroborate is used together with palladium (II) acetate, tris (dibenzylideneacetone)dipalladium (0) or bis(benzonitrile)dichloropalladium (II) in the reaction system.

Fluoroboric acid used as raw material in the production of the compounds (1) to (5) are corrosive and penetrate into the skin upon contact, and must be handled carefully. Furthermore, fluoroboric acid has acidity to corrode production utility made of stainless steel, and when hydrofluoric acid is liberated, it will corrode production utility made of glass. Therefore, the actual use of the above compounds in the production causes problems.

Alkylphosphonium tetraarylborate compounds are also developed, and the following compounds are known:

(6) triethylphosphonium tetraphenylborate (see Patent Document 1);

(7) tri-n-butylphosphonium tetraphenylborate (see Patent Document 1 and Nonpatent Document 6);

(8) tricyclohexylphosphonium tetraphenylborate (see Nonpatent Documents 4 and 7); and

(9) tri-tert-butylphosphonium tetraphenylborate (see Nonpatent Documents 4 and 7).

Nonpatent Documents 4, 6 and 7 describe the production of the alkylphosphonium tetraarylborate compounds. Specifically, the documents describe the following production processes (10) to (12).

(10) Tricyclohexylphosphine is reacted with fluoroboric acid to synthesize tricyclohexylphosphonium tetrafluoroborate, which is reacted with sodium tetraphenylborate to produce tricyclohexylphosphonium tetraphenylborate (75% yield). A similar process is described in which tri-tert-butylphosphine is used as starting material to produce tri-tert-butylphosphonium tetraphenylborate (71% yield) (see Nonpatent Document 4).

(11) Tri-tert-butylphosphine is reacted with 1,1,1,3,3,3-hexafluoro-2-propanol and with sodium tetraphenylborate to produce tri-tert-butylphosphonium tetraphenylborate (77% yield). A similar process is described in which tricyclohexylphosphine is used as starting material to produce tricyclohexylphosphonium tetraphenylborate (77% yield) (see Nonpatent Document 7).

(12) Tri-n-butylphosphine is reacted with hydrochloric acid in the presence of sodium tetraphenylborate to produce tri-n-butylphosphonium tetraphenylborate (53% yield) (see Nonpatent Document 6).

The four compounds (6) to (9) are the only compounds known as the alkylphosphonium tetraarylborate compounds, and the three processes (10) to (12) are the only known processes for producing them.

The processes (10) (Nonpatent Document 4) use fluoroboric acid and consequently have handling problems and problems of corrosion of production facility, and are not suited for industrial production.

The processes (11) (Nonpatent Document 7) use 1,1,1,3,3,3-hexafluoro-2-propanol which is expensive, and are not suited for industrial production. More inexpensive processes are desirable.

In the process (12) (Nonpatent Document 6) in which tri-n-butylphosphine is reacted with hydrochloric acid in the presence of sodium tetraphenylborate, the yield of tri-n-butylphosphonium tetraphenylborate is low (53% in terms of tri-n-butylphosphine). The reason for the low yield is not clear but is probably that a side reaction takes place between the reaction product of sodium tetraphenylborate with hydrochloric acid, and tri-n-butylphosphine.

The documents recited above do not describe that the carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions wherein the transition metal complexes having phosphine ligands produce catalytic effects, may be catalyzed by phosphonium tetraarylborate compounds together with transition metals, salts thereof, oxides thereof or complexes thereof in place of the transition metal complexes having phosphine ligands.

Thus, there is a need for the development of alkylphosphine derivatives that are producible without special reaction equipment and by simple operations, and have good handling properties.

Patent Document 1: JP-A-S62-149721 (pp. 2 and 3) Nonpatent Document 1: Journal of American Chemical Society (U.S.A.) (2000, vol. 122, No. 17, pp. 4020-4028)

Nonpatent Document 2: Catalog of Strem Chemicals, Inc.

Nonpatent Document 3: Journal of American Chemical Society (U.S.A.) (2002, vol. 124, No. 46, pp. 13662-13663)

Nonpatent Document 4: Journal of American Chemical Society (U.S.A.) (1991, vol. 113, No. 3, pp. 875-883)

Nonpatent Document 5: Organic Letters (U.S.A.) (2001, vol. 3, No. 26, pp. 4295-4298)

Nonpatent Document 6: Organometallics (U.S.A.) (1999, vol. 18, No. 20, pp. 3981-3990)

Nonpatent Document 7: Journal of American Chemical Society (U.S.A.) (1997, vol. 119, No. 16, pp. 3716-3731)

PROBLEMS TO BE SOLVED BY THE INVENTION

It is an object of the present invention to provide a novel process whereby a phosphonium borate compound is produced safely on an industrial scale, by simple reaction operations and in a high yield. It is another object of the invention to provide a novel phosphonium borate compound that is easily handled. It is a further object of the invention to provide a novel use of the phosphonium borate compound in combination with a transition metal, salt thereof, oxide thereof or complex thereof in the carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions wherein a transition metal complex having a phosphine ligand produces catalytic effects, wherein the phosphonium borate compound in combination with the transition metal, salt thereof, oxide thereof or complex thereof is used in place of the transition metal complex having a phosphine ligand.

SUMMARY OF THE INVENTION

The present inventors studied diligently to achieve the above objects, and they have found that a phosphonium borate compound can be produced safely, by simple reaction operations, and in a high yield by reacting a phosphine (II) with hydrochloric or sulfuric acid, and reacting the reaction product with a tetraarylborate compound (IV).

The inventors have also found a novel phosphonium borate compound which is highly resistance to oxidation as compared to alkylphosphine compounds. It has been also found that the phosphonium borate compound in combination with a transition metal, salt thereof, oxide thereof or complex thereof can be used in the carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions wherein a transition metal complex having a phosphine ligand produces catalytic effects, wherein the phosphonium borate compound in combination with the transition metal, salt thereof, oxide thereof or complex thereof is used in place of the transition metal complex having a phosphine ligand.

In a first aspect of the present invention, there is provided a process for producing a phosphonium borate compound, which comprises:

reacting a phosphine with HCl to produce a phosphine hydrochloride, the phosphine being represented by Formula (II):
(R¹)(R²)(R³)P (II)

wherein R¹is a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R¹, R²and R³may be the same or different from one another;

the phosphine hydrochloride being represented by Formula (III):
(R¹)(R²)(R³)PH.Cl (III)

wherein R¹, R²and R³are as defined in Formula (II);

and

reacting the phosphine hydrochloride with a tetraarylborate compound represented by Formula (IV):
M.BAr₄ (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms;

the phosphonium borate compound being represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹, R²and R³are as defined in Formula (II), and Ar is as defined in Formula (IV).

In a second aspect of the present invention, there is provided a process for producing a phosphonium borate compound, which comprises:

reacting a phosphine with H₂SO₄to produce a phosphine sulfate, the phosphine being represented by Formula (II):
(R¹)(R²)(R³)P (II)

wherein R¹is a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R¹, R²and R³may be the same or different from one another;

the phosphine sulfate being represented by Formula (V):
[(R¹)(R²)(R³)PH]_(2-n).H_nSO₄ (V)

wherein R¹, R²and R³are as defined in Formula (II), and n is an integer of 0 or 1;

and

reacting the phosphine sulfate with a tetraarylborate compound represented by Formula (IV):
M.BAr₄ (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms;

the phosphonium borate compound being represented by Formula (I) described above.

In a third aspect of the present invention, there is provided a novel phosphonium borate compound represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹is a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R¹, R²and R³may be the same or different from one another;

Ar is an aryl group of 6 to 20 carbon atoms;

R¹, R²and R³cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time; and

R¹, R²and R³cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time.

In a fourth aspect of the present invention, there is provided use of a phosphonium borate compound in combination with a transition metal, transition metal salt, transition metal oxide or transition metal complex in carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions wherein a transition metal complex having a phosphine ligand produces catalytic effects, wherein the phosphonium borate compound in combination with the transition metal, transition metal salt, transition metal oxide or transition metal complex is used in place of the transition metal complex having a phosphine ligand, the phosphonium borate compound being represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹is a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R¹, R²and R³may be the same or different from one another;

and

Ar is an aryl group of 6 to 20 carbon atoms.

The process according to the present invention can produce a phosphonium borate compound safely, by simple reaction operations and in a high yield. In the production process, the specific phosphine hydrochloride or phosphine sulfate is reacted with the specific tetraarylborate compound, and consequently the novel phosphonium borate compound is produced safely, by simple reaction operations and in a high yield. The phosphonium borate compound provided in the invention is novel. The phosphonium borate compound in combination with a transition metal, salt thereof, oxide thereof or complex thereof can be used in the carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions wherein a transition metal complex having a phosphine ligand produces catalytic effects, wherein the phosphonium borate compound in combination with the transition metal, salt thereof, oxide thereof or complex thereof is used in place of the transition metal complex having a phosphine ligand.

DETAILED DESCRIPTION OF THE INVENTION

The process for producing a phosphonium borate compound, novel phosphonium borate compound, and use of the compound will be described in detail hereinbelow.

Process for Producing Phosphonium Borate Compound

The process for producing a phosphonium borate compound will be described with reference to first and second production processes.

The first process for producing a phosphonium borate compound includes:

reacting a phosphine with HCl to produce a phosphine hydrochloride, the phosphine being represented by Formula (II):
(R¹)(R²)(R³)P (II)

wherein R¹is a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R¹, R²and R³may be the same or different from one another;

the phosphine hydrochloride being represented by Formula (III):
(R¹)(R²)(R³)PH.Cl (III)

wherein R¹, R²and R³are as defined in Formula (II);

and

reacting the phosphine hydrochloride with a tetraarylborate compound represented by Formula (IV):
M.BAr₄ (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms;

the phosphonium borate compound being represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹, R²and R³are as defined in Formula (II), and Ar is as defined in Formula (IV).

Specifically, the first process for producing a phosphonium borate compound (I) includes:

a 1st step in which the phosphine (II) is reacted with HCl to give the phosphine hydrochloride (III); and

a 2nd step in which the compound (III) is reacted with the tetraarylborate compound (IV) to produce the phosphonium borate compound (I), as illustrated in the reaction formula below:

The first production process can produce the phosphonium borate compound (I) in a high yield. The reason for this effect is not clear, but is probably that a side reaction that takes place when the compound (II), HCl and the compound (IV) are added at the same time can be substantially avoided.

The first process for producing a phosphonium borate compound (I) will be described below with reference to an embodiment 1 for producing the trialkylphosphonium tetraphenylborate and an embodiment 2 for producing the novel phosphonium borate compound.

Embodiment 1

[1st Step]

In the 1st step, a trialkylphosphine (II) and HCl are reacted under predetermined conditions. These components will be described below.

The trialkylphosphine (II) used as a raw material in the production process is represented by Formula (II):
(R¹)(R²)(R³)P (II)

wherein R¹, R²and R³are ethyl, n-butyl, tert-butyl or cyclohexyl groups, and are the same. Examples of the trialkylphosphines (II) include triethylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine and tricyclohexylphosphine.

The trialkylphosphines (II) of Formula (II) may be produced by or according to known methods.

Examples of such methods include, but are not limited to, reaction of phosphinas halides and organo Grignard reagents, reaction of phosphinas halides and organolithium reagents, and reaction of phosphines and olefins. The trialkylphosphines (II) synthesized by the above reactions may be purified prior to use, or may be used without purification.

The trialkylphosphines (II) may be used in an undiluted form, or may be diluted with a solvent. Herein, the diluting solvents include solvents contained in the unpurified trialkylphosphines (II). The unpurified trialkylphosphines (II) may be further diluted with a solvent.

The solvents are not particularly limited as long as they can dissolve reaction substrates and are inert to the reaction substrates. Examples thereof include water; alcohol solvents such as methanol, ethanol and octanol; aliphatic hydrocarbon solvents such as hexane, heptane and isooctane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ether solvents such as tetrahydrofuran and dibutyl ether; halogenated hydrocarbon solvents such as chloroform and tetrachloromethane; dimethylsulfoxide and dimethylformamide. The solvents may be used singly or in combination of two or more kinds.

HCl used in the production process may be hydrochloric acid or hydrogen chloride gas. The HCl concentration in hydrochloric acid is not particularly limited, and is desirably in the range of 0.1 to 37% by weight, preferably 10 to 37% by weight.

The 1st step involving the above raw materials is performed in a reactor purged with an inert gas such as nitrogen or argon. The addition sequence of the raw materials is not particularly limited. For example, HCl may be added to the trialkylphosphine (II), or the trialkylphosphine (II) may be added to HCl. When HCl is hydrochloric acid, the addition method is not particularly limited, and it may be added all at once or may be added dropwise intermittently or continuously. The hydrogen chloride gas may be easily added by being blown into the trialkylphosphine (II).

In the 1st step, the desirable HCl requirement, desirable temperature for smooth reaction, and desirable time to complete the reaction vary depending on the type of the trialkylphosphine (II) used, and are selected appropriately.

The HCl amount varies depending on the type of the trialkylphosphine (II), and is desirably in the range of 0.5 to 5 mol, preferably 0.8 to 1.6 mol per mol of phosphine. The HCl amount in this range enables the production of the trialkylphosphonium tetraphenylborate (I) in a high yield.

The reaction of HCl is desirably carried out while the solution is at −20 to 150° C., preferably 0 to 80° C. and is continuously stirred for up to 24 hours, preferably 30 minutes to 5 hours at the temperature. The reaction under these conditions enables the production of the trialkylphosphonium tetraphenylborate (I) in a high yield.

The completion of the reaction in the 1st step may be determined by confirming the absence of unreacted trialkylphosphine (II). Specifically, the organic phase is analyzed by gas chromatography or the like to determine the trialkylphosphine (II) in the organic phase. When the analysis confirms substantial absence of the remaining trialkylphosphine (II), the reaction is terminated. When the trialkylphosphine (II) is still present in the organic phase, the reaction is preferably continued.

The reaction solution takes various forms depending on the solvent used. For example, the solution may contain crystals of trialkylphosphine hydrochloride (III) (described later), may be a uniform solution or a suspension, or may be a two-phase system consisting of an aqueous phase and an organic phase. In the case of the two-phase system consisting of an aqueous phase and an organic phase, the system is subjected to separation. In the case of other solution forms, separation may be performed as required by adding water, toluene, n-hexane, n-heptane or the like. The aqueous phase resulting from the separation may be washed with toluene, n-hexane, n-heptane or the like as required.

The aqueous phase obtained by the reaction of the 1st step contains a reaction intermediate dissolved therein that is assumed to be a trialkylphosphine hydrochloride represented by Formula (III):
(R¹)(R²)(R³)PH.Cl (III)

wherein R¹, R²and R³are as defined in Formula (II).

The formation of the trialkylphosphine hydrochloride (III) may be confirmed by, for example, a nuclear magnetic resonance spectrum (¹H-NMR).

[2nd Step]

The reaction intermediate trialkylphosphine hydrochloride (III) obtained in the 1st step is reacted with a tetraphenylborate compound (IV) under predetermined conditions to produce a trialkylphosphonium tetraphenylborate represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹, R²and R³are ethyl, n-butyl, tert-butyl or cyclohexyl groups, and are the same; and Ar is phenyl group.

The tetraphenylborate compound (IV) used in the 2nd step is represented by Formula (IV):
M.BAr₄ (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is phenyl group.

In Formula (IV), M may be a magnesium halide or a calcium halide, with examples including magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, calcium fluoride, calcium chloride, calcium bromide and calcium iodide.

Specific examples of the tetraphenylborate compounds of Formula (IV) include lithium tetraphenylborate, sodium tetraphenylborate, potassium tetraphenylborate, tetraphenylborate magnesium fluoride, tetraphenylborate magnesium chloride, tetraphenylborate magnesium bromide, tetraphenylborate magnesium iodide, tetraphenylborate calcium fluoride, tetraphenylborate calcium chloride, tetraphenylborate calcium bromide and tetraphenylborate calcium iodide. The tetraphenylborate compounds (IV) may be used singly or in combination of two or more kinds.

Of the tetraphenylborate compounds (IV), sodium tetraphenylborate is particularly preferred. Sodium tetraphenylborate is preferable because of easy synthesis by known methods.

The tetraphenylborate compounds (IV) may be used in an undiluted form, or may be diluted with a solvent.

The solvent may be appropriately selected from the solvents used for dissolving the trialkylphosphines (II). The solvents may be used singly or in combination of two or more kinds.

Specifically, the 2nd step involving the above raw materials is performed by mixing the aqueous solution of the reaction intermediate assumed to be the trialkylphosphine hydrochloride (III), with the tetraphenylborate compound (IV) thereby to react the compound (III) with the compound (IV) under predetermined conditions.

The addition sequence of the aqueous solution obtained in the 1st step and the tetraphenylborate compound (IV) is not particularly limited. The addition method is not particularly limited, and the material may be added all at once or may be added dropwise intermittently or continuously.

In the 2nd step, the desirable requirement of the tetraphenylborate compound (IV), desirable temperature for smooth reaction, and desirable time to complete the reaction vary depending on the type of the raw material compound trialkylphosphine (II) used, amount of hydrogen chloride gas or hydrochloric acid, and type of the tetraphenylborate compound (IV), and are selected appropriately.

The amount of the tetraphenylborate compound (IV) varies depending on the type of the trialkylphosphine (II) used in the 1st step, and is desirably in the range of 0.55 to 5.5 mol, preferably 0.85 to 1.65mol per mol of phosphine. Particularly preferably, the compound is used in an amount of at least 1 mol per mol of HCl used. The amount of the tetraphenylborate compound (IV) in this range enables the production of the trialkylphosphonium tetraphenylborate (I) in a high yield.

The reaction of the tetraphenylborate compound (IV) is desirably carried out while the reaction solution is at −20 to 150° C., preferably 0 to 80° C. and is continuously stirred for up to 24 hours, preferably 1 to 5 hours at the temperature. The reaction under these conditions enables the production of the trialkylphosphonium tetraphenylborate (I) in a high yield.

After the completion of the reaction, purification such as recrystallization or column chromatography is performed, and consequently the objective trialkylphosphonium tetraphenylborate (I) of Formula (I) can be obtained with high purity:
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹, R²and R³are ethyl, n-butyl, tert-butyl or cyclohexyl groups, and are the same; and Ar is phenyl group.

According to the embodiment 1, the trialkylphosphonium tetraphenylborate (I) can be obtained in a high yield, specifically in a yield of about 87 to 93 mol % in terms of trialkylphosphine (II).

Examples of the trialkylphosphonium tetraphenylborates (I) of Formula (I) produced according to the embodiment 1 of the first production process include triethylphosphonium tetraphenylborate, tri-n-butylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate and tricyclohexylphosphonium tetraphenylborate.

Next, the embodiment 2 for producing the novel phosphonium borate compound will be described.

Embodiment 2

[1st Step]

In the 1st step, a phosphine (II) and HCl are reacted under predetermined conditions. These components will be described below.

The phosphine (II) used as a raw material in the production process is represented by Formula (II):
(R¹)(R²)(R³)P (II)

In Formula (II), R¹is as described below.

R¹may be a secondary alkyl group, desirably a secondary alkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The secondary alkyl groups include isopropyl, sec-butyl, 2-pentyl, 3-pentyl, 2-hexyl and 3-hexyl.

R¹may be a tertiary alkyl group, desirably a tertiary alkyl group having 4 to 20, preferably 4 to 11 carbon atoms. The tertiary alkyl groups include tert-butyl, tert-amyl, 1,1-dimethylbutyl, 3-methyl-3-pentyl and 1,1,2-trimethylpropyl.

R¹may be a cycloalkyl group, desirably a cycloalkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-adamantyl, 2-methyl-1-adamantyl, 2-adamantyl, 1-methyl-2-adamantyl and 2-methyl-2-adamantyl. R¹is not limited to the groups described above.

In Formula (II), R²is as described below.

R²may be a primary alkyl group, desirably a primary alkyl group having 1 to 20, preferably 1 to 8 carbon atoms. The primary alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-methyl-1-pentyl, 2,2-diethyl-1-ethyl, n-heptyl and n-octyl.

R²may be a secondary alkyl group, desirably a secondary alkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The secondary alkyl groups include isopropyl, sec-butyl, 2-pentyl, 3-pentyl, 2-hexyl and 3-hexyl.

R²may be a tertiary alkyl group, desirably a tertiary alkyl group having 4 to 20, preferably 4 to 11 carbon atoms. The tertiary alkyl groups include tert-butyl, tert-amyl, 1,1-dimethylbutyl, 3-methyl-3-pentyl and 1,1,2-trimethylpropyl.

R²may be a cycloalkyl group, desirably a cycloalkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-adamantyl, 2-methyl-1-adamantyl, 2-adamantyl, 1-methyl-2-adamantyl and 2-methyl-2-adamantyl.

R²may be an aralkyl group, desirably an aralkyl group having 7 to 20, preferably 7 to 12 carbon atoms. The aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 2-ethenylbenzyl, 3-ethenylbenzyl, 4-ethenylbenzyl, 4-(2-ethenylphenyl)butyl, 4-(3-ethenylphenyl)butyl and 4-(4-ethenylphenyl)butyl.

R²may desirably be an allyl group having 3 to 20, preferably 3 to 8 carbon atoms. The allyl groups include allyl and 2-octenyl. R²is not limited to the groups described above.

In Formula (II), R³is as described below.

R³may be a primary alkyl group, desirably a primary alkyl group having 1 to 20, preferably 1 to 8 carbon atoms. The primary alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-methyl-1-pentyl, 2,2-diethyl-1-ethyl, n-heptyl and n-octyl.

R³may be a secondary alkyl group, desirably a secondary alkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The secondary alkyl groups include isopropyl, sec-butyl, 2-pentyl, 3-pentyl, 2-hexyl and 3-hexyl.

R³may be a tertiary alkyl group, desirably a tertiary alkyl group having 4 to 20, preferably 4 to 11 carbon atoms. The tertiary alkyl groups include tert-butyl, tert-amyl, 1,1-dimethylbutyl, 3-methyl-3-pentyl and 1,1,2-trimethylpropyl.

R³may be a cycloalkyl group, desirably a cycloalkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-adamantyl, 2-methyl-1-adamantyl, 2-adamantyl, 1-methyl-2-adamantyl and 2-methyl-2-adamantyl.

R³may be an aryl group, desirably an aryl group having 6 to 30, preferably 6 to 22 carbon atoms. The aryl groups include phenyl, ortho-tolyl, meta-tolyl, para-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, mesityl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2-ethenylphenyl, 3-ethenylphenyl, 4-ethenylphenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 1,1′-binaphthalene-2-yl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-tert-butoxyphenyl, 3-tert-butoxyphenyl, 4-tert-butoxyphenyl, 2-dimethylaminophenyl, 3-dimethylaminophenyl, 4-dimethylaminophenyl, 2′-dimethylamino-2-biphenylyl, 8-dimethylamino-1-naphthyl and 2′-dimethylamino-1,1′-binaphthalene-2-yl.

R³may be an aralkyl group, desirably an aralkyl group having 7 to 20, preferably 7 to 12-carbon atoms. The aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 2-ethenylbenzyl, 3-ethenylbenzyl, 4-ethenylbenzyl, 4-(2-ethenylphenyl)butyl, 4-(3-ethenylphenyl)butyl and 4-(4-ethenylphenyl)butyl.

R³may be an alkenyl group, desirably an alkenyl group having 2 to 20, preferably 2 to 8 carbon atoms. The alkenyl groups include vinyl, methallyl and 1-octenyl.

R³may be an alkynyl group, desirably an alkynyl group having 2 to 20, preferably 2 to 8 carbon atoms. The alkynyl groups include ethynyl, 1-propynyl and 1-octynyl.

R³may desirably be an allyl group having 3 to 20, preferably 3 to 8 carbon atoms. The allyl groups include allyl and 2-octenyl. R³is not limited to the groups described above.

As long as R¹, R²and R³are selected from the above groups, they may have an arbitrary combination in terms of carbon atom numbers.

Specific examples of the phosphines (II) represented by Formula (II) are shown in Tables 1-1 to 4-2 which will be presented later.

Specifically, preferred phosphines (II) include di-tert-butylmethylphosphine, tri-tert-butylphosphine, di-tert-butylethylphosphine, n-butyl-di-tert-butylphosphine, n-butyl-dicyclohexylphosphine, sec-butyl-di-tert-butylphosphine, cyclohexyl-di-tert-butylphosphine, di-tert-butyl-n-octylphosphine, di-tert-butylphenylphosphine, 2-biphenylyl-di-tert-butylphosphine, di-tert-butyl-1-naphthylphosphine, benzyl-di-tert-butylphosphine, di-tert-butyl(4-ethenylbenzyl)phosphine, di-tert-butylvinylphosphine, allyl-di-tert-butylphosphine, tricyclopentylphosphine, tricyclohexylphosphine and triisopropylphosphine. Di-tert-butylmethylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine and triisopropylphosphine are more preferable. These phosphines (II) are preferable because of easy availability of raw materials.

The phosphine compounds of Formula (II) may be produced by or according to known methods.

Examples of such methods include, but are not limited to, reaction of phosphinas halides and organo Grignard reagents, reaction of phosphinas halides and organolithium reagents, and reaction of phosphines and olefins. The phosphines (II) synthesized by the above reactions may be purified prior to use, or may be used without purification.

The phosphines (II) may be used in an undiluted form, or may be diluted with a solvent. Herein, the diluting solvents include solvents contained in the unpurified phosphines (II). The unpurified phosphines (II) may be further diluted with a solvent.

The solvents are not particularly limited as long as they can dissolve reaction substrates and are inert to the reaction substrates. Examples thereof include water; alcohol solvents such as methanol, ethanol and octanol; aliphatic hydrocarbon solvents such as hexane, heptane and isooctane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ether solvents such as tetrahydrofuran and dibutyl ether; halogenated hydrocarbon solvents such as chloroform and tetrachloromethane; dimethylsulfoxide and dimethylformamide. The solvents may be used singly or in combination of two or more kinds.

HCl used in the production process may be hydrochloric acid or hydrogen chloride gas. The HCl concentration in hydrochloric acid is not particularly limited, and is desirably in the range of 0.1 to 37% by weight, preferably 10 to 37% by weight.

The 1st step involving the above raw materials is performed in a reactor purged with an inert gas such as nitrogen or argon. The addition sequence of the raw materials is not particularly limited. For example, HCl may be added to the phosphine (II), or the phosphine (II) may be added to HCl. When HCl is hydrochloric acid, the addition method is not particularly limited, and it may be added all at once or may be added dropwise intermittently or continuously. The hydrogen chloride gas may be easily added by being blown into the phosphine (II).

In the 1st step, the desirable HCl requirement, desirable temperature for smooth reaction, and desirable time to complete the reaction vary depending on the type of the phosphine (II) used, and are selected appropriately.

The HCl amount varies depending on the type of the phosphine (II), and is desirably in the range of 0.5 to 5 mol, preferably 0.8 to 1.6 mol per mol of phosphine. The HCl amount in this range enables the production of the phosphonium borate compound (I) in a high yield.

The reaction of HCl is desirably carried out while the solution is at −20 to 150° C., preferably 0 to 80° C. and is continuously stirred for up to 24 hours, preferably 30 minutes to 5 hours at the temperature. The reaction under these conditions enables the production of the phosphonium borate compound (I) in a high yield.

The completion of the reaction in the 1st step may be determined by confirming the absence of unreacted phosphine (II). Specifically, the organic phase is analyzed by gas chromatography or the like to determine the phosphine (II) in the organic phase. When the analysis confirms substantial absence of the remaining phosphine (II), the reaction is terminated. When the phosphine is still present in the organic phase, the reaction is preferably continued.

The reaction solution takes various forms depending on the solvent used. For example, the solution may contain crystals of phosphine hydrochloride (III) (described later), may be a uniform solution or a suspension, or may be a two-phase system consisting of an aqueous phase and an organic phase. In the case of the two-phase system consisting of an aqueous phase and an organic phase, the phosphine hydrochloride (III) passes into the aqueous phase and therefore the aqueous phase is subjected to separation. In the case of other solution forms, separation may be performed as required by adding water, toluene, n-hexane, n-heptane or the like. The aqueous phase resulting from the separation may be washed with toluene, n-hexane, n-heptane or the like as required.

The aqueous phase obtained by the reaction of the 1st step contains a reaction intermediate dissolved therein that is assumed to be a phosphine hydrochloride (III) represented by Formula (III):
(R¹)(R²)(R³)PH.Cl (III)

wherein R¹, R²and R³are as defined in Formula (II).

The formation of the phosphine hydrochloride (III) may be confirmed by, for example, a nuclear magnetic resonance spectrum (¹H-NMR)

[2nd Step]

The reaction intermediate that is assumed to be the phosphine hydrochloride (III) obtained in the 1st step is reacted with a tetraarylborate compound (IV) under predetermined conditions to produce a novel phosphonium borate compound (I) of the present invention.

The tetraarylborate compound (IV) used in the 2nd step is represented by Formula (IV):
M.BAr₄ (IV)

In Formula (IV), M may be a magnesium halide or a calcium halide, with examples including magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, calcium fluoride, calcium chloride, calcium bromide and calcium iodide.

Ar is desirably an aryl group having 6 to 20, preferably 6 to 10 carbon atoms. Specific examples include phenyl, ortho-tolyl, meta-tolyl, para-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, mesityl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-tert-butoxyphenyl, 3-tert-butoxyphenyl and 4-tert-butoxyphenyl.

The tetraarylborate compound (IV) is selected appropriately such that in the phosphonium borate compound (I) of Formula (I), R¹, R²and R³are not tert-butyl groups simultaneously and Ar is not phenyl group at the same time, and R¹, R²and R³are not cyclohexyl groups simultaneously and Ar is not phenyl group at the same time.

Specific examples of the tetraarylborate compounds represented by Formula (IV) are shown in Tables 5 to 10 which will be presented later. These tetraarylborate compounds may be used singly or in combination of two or more kinds.

Of the tetraarylborate compounds (IV), sodium tetraphenylborate and sodium tetra-para-tolylborate are particularly preferable. The tetraarylborate compounds (IV) are preferable because of easy synthesis by known methods.

The tetraarylborate compounds (IV) may be used in an undiluted form, or may be diluted with a solvent.

The solvent may be appropriately selected from the solvents used for dissolving the phosphines (II). The solvents may be used singly or in combination of two or more kinds.

Specifically, the 2nd step involving the above raw materials is performed by mixing the aqueous solution of the reaction intermediate assumed to be the phosphine hydrochloride (III), with the tetraarylborate compound (IV) thereby to react the compound (III) with the compound (IV) under predetermined conditions.

The addition sequence of the aqueous solution obtained in the 1st step and the tetraarylborate compound (IV) is not particularly limited. The addition method is not particularly limited, and the material may be added all at once or may be added dropwise intermittently or continuously.

In the 2nd step, the desirable requirement of the tetraarylborate compound (IV), desirable temperature for smooth reaction, and desirable time to complete the reaction vary depending on the type of the raw material compound phosphine (II) used, amount of hydrogen chloride gas or hydrochloric acid, and type of the tetraarylborate compound (IV), and are selected appropriately.

The amount of the tetraarylborate compound (IV) varies depending on the type of the phosphine (II) used in the 1st step, and is desirably in the range of 0.55 to 5.5 mol, preferably 0.85 to 1.65 mol per mol of phosphine. Particularly preferably, the compound is used in an amount of at least 1 mol per mol of HCl used. The amount of the tetraarylborate compound (IV) in this range enables the production of the phosphonium borate compound (I) in a high yield.

The reaction of the tetraarylborate compound (IV) is desirably carried out while the reaction solution is at −20 to 150° C., preferably 0 to 80° C. and is continuously stirred for up to 24 hours, preferably 1 to 5 hours at the temperature. The reaction under these conditions enables the production of the phosphonium borate compound (I) in a high yield.

After the completion of the reaction, purification such as recrystallization or column chromatography is performed, and consequently the objective novel phosphonium borate compound (I) of Formula (I) can be obtained with high purity:
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹, R²and R³are as defined in Formula (II); Ar is as defined in Formula (IV); R¹, R²and R³cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time; and R¹, R²and R³cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time.

According to the embodiment 2, the novel phosphonium borate compound (I) can be obtained in a high yield, specifically in a yield of about 76 to 89 mol % in terms of phosphine (II).

The novel phosphonium borate compound produced according to the embodiment 2 of the first production process will be described later.

The second process for producing a phosphonium borate compound includes:

reacting a phosphine with H₂SO₄to produce a phosphine sulfate, the phosphine being represented by Formula (II):
(R¹)(R²)(R³)P (II)

wherein R¹is a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R¹, R²and R³may be the same or different from one another;

the phosphine sulfate being represented by Formula (V):
[(R¹)(R²)(R³)PH]_(2-n).H_nSO₄ (V)

wherein R¹, R²and R³are as defined in Formula (II), and n is an integer of 0 or 1;

and

reacting the phosphine sulfate with a tetraarylborate compound represented by Formula (IV):
M.BAr₄ (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms;

the phosphonium borate compound being represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹, R²and R³are as defined in Formula (II), and Ar is as defined in Formula (IV).

Specifically, the second process for producing a phosphonium borate compound (I) includes:

a 1'st step in which the phosphine (II) is reacted with H₂SO₄to give the phosphine sulfate (V); and

a 2'nd step in which the compound (V) is reacted with the tetraarylborate compound (IV) to produce the phosphonium borate compound (I), as illustrated in the reaction formula below:

The second production process can produce the phosphonium borate compound (I) in a high yield. The reason for this effect is not clear, but is probably that a side reaction that takes place when the compound (II), H₂SO₄and the compound (IV) are added at the same time can be substantially avoided.

The second process for producing a phosphonium borate compound (I) will be described below with reference to an embodiment 1 for producing the trialkylphosphonium tetraphenylborate and an embodiment 2 for producing the novel phosphonium borate compound.

Embodiment 1

[1'st Step]

In the 1'st step, a trialkylphosphine (II) and H₂SO₄are reacted under predetermined conditions.

These components will be described below.

The trialkylphosphine (II) used as a raw material in the production process is represented by Formula (II):
(R¹)(R²)(R³)P (II)

wherein R¹, R²and R³are ethyl, n-butyl, tert-butyl or cyclohexyl groups, and are the same. Examples of the trialkylphosphines (II) include those described in the embodiment 1 of the first production process.

H₂SO₄used in the production process may be sulfuric acid. The concentration thereof is not particularly limited, and is desirably in the range of 0.1 to 95% by weight, preferably 10 to 40% by weight.

The 1'st step involving the above raw materials is performed in a reactor purged with an inert gas such as nitrogen or argon. The addition sequence of the raw materials is not particularly limited. For example, sulfuric acid may be added to the trialkylphosphine (II), or the trialkylphosphine (II) may be added to sulfuric acid. The addition method is not particularly limited, and the material may be added all at once or may be added dropwise intermittently or continuously.

In the 1'st step, the desirable H₂SO₄requirement, desirable temperature for smooth reaction, and desirable time to complete the reaction vary depending on the type of the trialkylphosphine (II) used, and are selected appropriately.

The H₂SO₄amount varies depending on the type of the trialkylphosphine (II), and is desirably in the range of 0.25 to 2.5 mol, preferably 0.4 to 0.8 mol per mol of phosphine. The H₂SO₄amount in this range enables the production of the trialkylphosphonium tetraphenylborate (I) in a high yield.

The reaction of sulfuric acid is desirably carried out while the solution is at −20 to 150° C., preferably 0 to 80° C. and is continuously stirred for up to 24 hours, preferably 30 minutes to 5 hours at the temperature. The reaction under these conditions enables the production of the trialkylphosphonium tetraphenylborate (I) in a high yield.

The completion of the reaction in the 1'st step may be determined by confirming the absence of unreacted trialkylphosphine (II). Specifically, the organic phase is analyzed by gas chromatography or the like to determine the trialkylphosphine (II) in the organic phase. When the analysis confirms substantial absence of the remaining trialkylphosphine (II), the reaction is terminated. When the trialkylphosphine (II) is still present in the organic phase, the reaction is preferably continued.

The reaction solution takes various forms depending on the solvent used. For example, the solution may contain crystals of trialkylphosphine sulfate (V) (described later), may be a uniform solution or a suspension, or may be a two-phase system consisting of an aqueous phase and an organic phase. In the case of the two-phase system consisting of an aqueous phase and an organic phase, the system is subjected to separation. In the case of other solution forms, separation may be performed as required by adding water, toluene, n-hexane, n-heptane or the like. The aqueous phase resulting from the separation may be washed with toluene, n-hexane, n-heptane or the like as required.

The aqueous phase obtained by the reaction of the 1'st step contains a reaction intermediate dissolved therein that is assumed to be a trialkylphosphine sulfate (V) represented by Formula (V):
[(R¹)(R²)(R³)PH]_(2-n).H_nSO₄ (V)

wherein R¹, R²and R³are as defined in Formula (II), and n is an integer of 0 or 1.

The formation of the trialkylphosphine sulfate (V) may be confirmed by, for example, a nuclear magnetic resonance spectrum (¹H-NMR).

[2'nd Step]

The reaction intermediate trialkylphosphine sulfate (V) obtained in the 1'st step is reacted with a tetraphenylborate compound (IV) under predetermined conditions to produce a trialkylphosphonium tetraphenylborate represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹, R²and R³are ethyl, n-butyl, tert-butyl or cyclohexyl groups, and are the same; and Ar is phenyl group.

The tetraphenylborate compound (IV) used in the 2'nd step is represented by Formula (IV):
M.BAr₄ (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is phenyl group. Examples thereof include those described in the embodiment 1 of the first production process.

Specifically, the 2'nd step involving the above raw materials is performed by mixing the aqueous solution of the reaction intermediate assumed to be the trialkylphosphine sulfate (V), with the tetraphenylborate compound (IV) thereby to react the compound (V) with the compound (IV) under predetermined conditions.

The addition sequence of the aqueous solution obtained in the 1'st step and the tetraphenylborate compound (IV) is not particularly limited. The addition method is not particularly limited, and the material may be added all at once or may be added dropwise intermittently or continuously.

In the 2'nd step, the desirable requirement of the tetraphenylborate compound (IV), desirable temperature for smooth reaction, and desirable time to complete the reaction vary depending on the type of the raw material compound trialkylphosphine (II) used, amount of sulfuric acid, and type of the tetraphenylborate compound (IV), and are selected appropriately.

The amount of the tetraphenylborate compound (IV) varies depending on the type of the trialkylphosphine (II) used in the 1'st step, and is desirably in the range of 0.55 to 5.5 mol, preferably 0.85 to 1.65 mol per mol of phosphine. Particularly preferably, the compound is used in an amount of at least 2 mol per mol of H₂SO₄used. The amount of the tetraphenylborate compound (IV) in this range enables the production of the trialkylphosphonium tetraphenylborate (I) in a high yield.

The reaction of the tetraphenylborate compound (IV) is desirably carried out while the reaction solution is at −20 to 150° C., preferably 0 to 80° C. and is continuously stirred for up to 24 hours, preferably 1 to 5 hours at the temperature. The reaction under these conditions enables the production of the trialkylphosphonium tetraphenylborate (I) in a high yield.

After the completion of the reaction, purification such as recrystallization or column chromatography is performed, and consequently the objective trialkylphosphonium tetraphenylborate (I) of Formula (I) can be obtained with high purity:
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹, R²and R³are ethyl, n-butyl, tert-butyl or cyclohexyl groups, and are the same; and Ar is phenyl group.

According to the embodiment 1, the trialkylphosphonium tetraphenylborate (I) can be obtained in a high yield, specifically in a yield of about 87 to 93 mol % in terms of trialkylphosphine (II).

Examples of the trialkylphosphonium tetraphenylborates (I) of Formula (I) produced according to the embodiment 1 of the second production process include triethylphosphonium tetraphenylborate, tri-n-butylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenylborate and tricyclohexylphosphonium tetraphenylborate.

Next, the embodiment 2 for producing the novel phosphonium borate compound will be described.

Embodiment 2

[1'st Step]

In the 1'st step, a phosphine (II) and H₂SO₄are reacted under predetermined conditions. These components will be described below.

The phosphine (II) used as a raw material in the production process is represented by Formula (II):
(R¹)(R²)(R³)P (II)

wherein R¹is a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R¹, R²and R³may be the same or different from one another. Examples of the phosphines (II) include those described in the embodiment 2 of the first production process.

H₂SO₄may be sulfuric acid. The concentration thereof is not particularly limited, and is desirably in the range of 0.1 to 95% by weight, preferably 10 to 40% by weight.

The 1'st step involving the above raw materials is performed in a reactor purged with an inert gas such as nitrogen or argon. The addition sequence of the raw materials is not particularly limited. For example, sulfuric acid may be added to the phosphine (II), or the phosphine (II) may be added to sulfuric acid. The addition method is not particularly limited, and the material may be added all at once or may be added dropwise intermittently or continuously.

In the 1'st step, the desirable H₂SO₄requirement, desirable temperature for smooth reaction, and desirable time to complete the reaction vary depending on the type of the phosphine (II) used, and are selected appropriately.

The amount of sulfuric acid varies depending on the type of the phosphine (II), and is desirably in the range of 0.25 to 2.5 mol, preferably 0.4 to 0.8 mol per mol of phosphine. The H₂SO₄amount in this range enables the production of the phosphonium borate compound (I) in a high yield.

The reaction of H₂SO₄is desirably carried out while the solution is at −20 to 150° C., preferably 0 to 80° C. and is continuously stirred for up to 24 hours, preferably 30 minutes to 5 hours at the temperature. The reaction under these conditions enables the production of the phosphonium borate compound (I) in a high yield.

The completion of the reaction in the 1'st step may be determined by confirming the absence of unreacted phosphine (II). Specifically, the organic phase is analyzed by gas chromatography or the like to determine the phosphine (II) in the organic phase. When the analysis confirms substantial absence of the remaining phosphine (II), the reaction is terminated. When the phosphine is still present in the organic phase, the reaction is preferably continued.

The reaction solution takes various forms depending on the solvent used. For example, the solution may contain crystals of phosphine sulfate (V) (described later), may be a uniform solution or a suspension, or may be a two-phase system consisting of an aqueous phase and an organic phase. In the case of the two-phase system consisting of an aqueous phase and an organic phase, the phosphine sulfate (V) passes into the aqueous phase and therefore the aqueous phase is subjected to separation. In the case of other solution forms, separation may be performed as required by adding water, toluene, n-hexane, n-heptane or the like. The aqueous phase resulting from the separation may be washed with toluene, n-hexane, n-heptane or the like as required.

The aqueous phase obtained by the reaction of the 1'st step contains a reaction intermediate dissolved therein that is assumed to be a phosphine sulfate (V) represented by Formula (V):
[(R¹)(R²)(R³)PH]_(2-n).H_nSO₄ (V)

wherein R¹, R²and R³are as defined in Formula (II), and n is an integer of 0 or 1.

The formation of the phosphine sulfate (V) may be confirmed by, for example, a nuclear magnetic resonance spectrum (¹H-NMR).

[2'nd Step]

The reaction intermediate that is assumed to be the phosphine sulfate (V) obtained in the 1'st step is reacted with a tetraarylborate compound (IV) under predetermined conditions to produce a phosphonium borate compound (I) of the present invention.

The tetraarylborate compound (IV) used in the 2'nd step is represented by Formula (IV):
M.BAr₄ (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms. Examples of the tetraarylborate compounds include those described in the embodiment 2 of the first production process.

Specifically, the 2'nd step involving the above raw materials is performed by mixing the aqueous solution of the reaction intermediate assumed to be the phosphine sulfate (V), with the tetraarylborate compound (IV) thereby to react the compound (V) with the compound (IV) under predetermined conditions.

The addition sequence of the aqueous solution obtained in the 1'st step and the tetraarylborate compound (IV) is not particularly limited. The addition method is not particularly limited, and the material may be added all at once or may be added dropwise intermittently or continuously.

In the 2'nd step, the desirable requirement of the tetraarylborate compound (IV), desirable temperature for smooth reaction, and desirable time to complete the reaction vary depending on the type of the raw material compound phosphine (II) used, amount of sulfuric acid, and type of the tetraarylborate compound (IV), and are selected appropriately.

The amount of the tetraarylborate compound (IV) varies depending on the type of the phosphine (II) used in the 1'st step, and is desirably in the range of 0.55 to 5.5 mol, preferably 0.85 to 1.65 mol per mol of phosphine. Particularly preferably, the compound is used in an amount of at least 2 mol per mol of H₂SO₄used. The amount of the tetraarylborate compound (IV) in this range enables the production of the phosphonium borate compound (I) in a high yield.

The reaction of the tetraarylborate compound (IV) is desirably carried out while the reaction solution is at −20 to 150° C., preferably 0 to 80° C. and is continuously stirred for up to 24 hours, preferably 1 to 5 hours at the temperature. The reaction under these conditions enables the production of the phosphonium borate compound (I) in a high yield.

After the completion of the reaction, purification such as recrystallization or column chromatography is performed, and consequently the objective novel phosphonium borate compound (I) of Formula (I) can be obtained with high purity.

The second production process can produce the novel phosphonium borate compound (I) in a high yield, specifically in a yield of about 80 to 85 mol % in terms of phosphine (II).

Novel Phosphonium Borate Compound

The novel phosphonium borate compound (I) of the present invention may be produced according to the embodiment 2 of the first production process and according to the embodiment 2 of the second production process. The phosphonium borate compound is represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹is a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R¹, R²and R³may be the same or different from one another;

Ar is an aryl group of 6 to 20 carbon atoms;

R¹, R²and R³are not tert-butyl groups simultaneously and Ar is not phenyl group at the same time; and

R¹, R²and R³are not cyclohexyl groups simultaneously and Ar is not phenyl group at the same time.

R¹

In Formula (I), R¹is as described below.

R¹may be a secondary alkyl group, desirably a secondary alkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The secondary alkyl groups include isopropyl, sec-butyl, 2-pentyl, 3-pentyl, 2-hexyl and 3-hexyl.

R¹may be a tertiary alkyl group, desirably a tertiary alkyl group having 4 to 20, preferably 4 to 11 carbon atoms. The tertiary alkyl groups include tert-butyl, tert-amyl, 1,1-dimethylbutyl, 3-methyl-3-pentyl and 1,1,2-trimethylpropyl.

R¹may be a cycloalkyl group, desirably a cycloalkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-adamantyl, 2-methyl-1-adamantyl, 2-adamantyl, 1-methyl-2-adamantyl and 2-methyl-2-adamantyl. R¹is not limited to the groups described above.

R²

In Formula (I), R²is as described below.

R²may be a primary alkyl group, desirably a primary alkyl group having 1 to 20, preferably 1 to 8 carbon atoms. The primary alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-methyl-1-pentyl, 2,2-diethyl-1-ethyl, n-heptyl and n-octyl.

R²may be a secondary alkyl group, desirably a secondary alkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The secondary alkyl groups include isopropyl, sec-butyl, 2-pentyl, 3-pentyl, 2-hexyl and 3-hexyl.

R²may be a tertiary alkyl group, desirably a tertiary alkyl group having 4 to 20, preferably 4 to 11 carbon atoms. The tertiary alkyl groups include tert-butyl, tert-amyl, 1,1-dimethylbutyl, 3-methyl-3-pentyl and 1,1,2-trimethylpropyl.

R²may be a cycloalkyl group, desirably a cycloalkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-adamantyl, 2-methyl-1-adamantyl, 2-adamantyl, 1-methyl-2-adamantyl and 2-methyl-2-adamantyl.

R²may be an aralkyl group, desirably an aralkyl group having 7 to 20, preferably 7 to 12 carbon atoms. The aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 2-ethenylbenzyl, 3-ethenylbenzyl, 4-ethenylbenzyl, 4-(2-ethenylphenyl)butyl, 4-(3-ethenylphenyl)butyl and 4-(4-ethenylphenyl) butyl.

R²may desirably be an allyl group having 3 to 20, preferably 3 to 8 carbon atoms. The allyl groups include allyl and 2-octenyl. R²is not limited to the groups described above.

R³

In Formula (I), R³is as described below.

R³may be a primary alkyl group, desirably a primary alkyl group having 1 to 20, preferably 1 to 8 carbon atoms. The primary alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-methyl-1-pentyl, 2,2-diethyl-1-ethyl, n-heptyl and n-octyl.

R³may be a secondary alkyl group, desirably a secondary alkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The secondary alkyl groups include isopropyl, sec-butyl, 2-pentyl, 3-pentyl, 2-hexyl and 3-hexyl.

R³may be a tertiary alkyl group, desirably a tertiary alkyl group having 4 to 20, preferably 4 to 11 carbon atoms. The tertiary alkyl groups include tert-butyl, tert-amyl, 1,1-dimethylbutyl, 3-methyl-3-pentyl and 1,1,2-trimethylpropyl.

R³may be a cycloalkyl group, desirably a cycloalkyl group having 3 to 20, preferably 3 to 11 carbon atoms. The cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-adamantyl, 2-methyl-1-adamantyl, 2-adamantyl, 1-methyl-2-adamantyl and 2-methyl-2-adamantyl.

R³may be an aryl group, desirably an aryl group having 6 to 30, preferably 6 to 22 carbon atoms. The aryl groups include phenyl, ortho-tolyl, meta-tolyl, para-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, mesityl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2-ethenylphenyl, 3-ethenylphenyl, 4-ethenylphenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, 1,1′-binaphthalene-2-yl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-tert-butoxyphenyl, 3-tert-butoxyphenyl, 4-tert-butoxyphenyl, 2-dimethylaminophenyl, 3-dimethylaminophenyl, 4-dimethylaminophenyl, 2′-dimethylamino-2-biphenylyl, 8-dimethylamino-1-naphthyl and 2′-dimethylamino-1,1′-binaphthalene-2-yl.

R³may be an aralkyl group, desirably an aralkyl group having 7 to 20, preferably 7 to 12 carbon atoms. The aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 2-ethenylbenzyl, 3-ethenylbenzyl, 4-ethenylbenzyl, 4-(2-ethenylphenyl)butyl, 4-(3-ethenylphenyl)butyl and 4-(4-ethenylphenyl)butyl.

R³may be an alkenyl group, desirably an alkenyl group having 2 to 20, preferably 2 to 8 carbon atoms. The alkenyl groups include vinyl, methallyl and 1-octenyl.

R³may be an alkynyl group, desirably an alkynyl group having 2 to 20, preferably 2 to 8 carbon atoms. The alkynyl groups include ethynyl, 1-propynyl and 1-octynyl.

R³may desirably be an allyl group having 3 to 20, preferably 3 to 8 carbon atoms. The allyl groups include allyl and 2-octenyl. R³is not limited to the groups described above.

As long as R¹, R²and R³are selected from the above groups, they may have an arbitrary combination in terms of carbon atom numbers.

Ar

In Formula (I), Ar is desirably an aryl group of 6 to 20, preferably 6 to 10 carbon atoms.

The aryl groups include phenyl, ortho-tolyl, meta-tolyl, para-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, mesityl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-tert-butoxyphenyl, 3-tert-butoxyphenyl and 4-tert-butoxyphenyl. Ar is not limited to the groups described above.

In Formula (I), R¹, R²and R³cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time, and R¹, R²and R³cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time.

The novel phosphonium borate compound preferably has Formula (I) given below for the reason that the raw material phosphine (II) and tetraarylborate compound (IV) can be synthesized easily by known methods:
(R¹)(R²)(R³)PH.BAr₄ (I)

wherein R¹is a secondary alkyl group of 3 to 6 carbon atoms, a tertiary alkyl group of 4 to 8 carbon atoms, or a cycloalkyl group of 3 to 8 carbon atoms;

R²is a hydrogen atom, a primary alkyl group of 1 to 8 carbon atoms, a secondary alkyl group of 3 to 6 carbon atoms, a tertiary alkyl group of 4 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aralkyl group of 7 to 9 carbon atoms, or an allyl group of 3 to 4 carbon atoms;

R³is a hydrogen atom, a primary alkyl group of 1 to 8 carbon atoms, a secondary alkyl group of 3 to 6 carbon atoms, a tertiary alkyl group of 4 to 8 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, an aryl group of 6 to 15 carbon atoms, an aralkyl group of 7 to 9 carbon atoms, an alkenyl group of 2 to 4 carbon atoms, an alkynyl group of 2 to 4 carbon atoms, or an allyl group of 3 to 4 carbon atoms;

R¹, R²and R³may be the same or different from one another;

Ar is an aryl group of 6 to 10 carbon atoms;

R¹, R²and R³cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time; and

R¹, R²and R³cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time.

Specific examples of the novel phosphonium borate compounds (I) represented by Formula (I) are shown in Tables 11-1 to 18-3 which will be presented later.

Of the phosphonium borate compounds (I), preferred are:

(1) di-tert-butylmethylphosphonium tetraphenylborate,
(2) di-tert-butylmethylphosphonium tetra-para-tolylborate,
(3) tri-tert-butylphosphonium tetra-para-tolylborate,
(4) di-tert-butylethylphosphonium tetraphenylborate,
(5) n-butyl-di-tert-butylphosphonium tetraphenylborate,
(6) sec-butyl-di-tert-butylphosphonium tetraphenylborate,
(7) cyclohexyl-di-tert-butylphosphonium tetraphenylborate,
(8) di-tert-butyl-n-octylphosphonium tetraphenylborate,
(9) di-tert-butylphenylphosphonium tetraphenylborate,
(10) 2-biphenylyl-di-tert-butylphosphonium tetraphenylborate,
(11) di-tert-butyl-1-naphthylphosphonium tetraphenylborate,
(12) benzyl-di-tert-butylphosphonium tetraphenylborate,
(13) di-tert-butyl(4-ethenylbenzyl)phosphonium tetraphenylborate,
(14) di-tert-butylvinylphosphonium tetraphenylborate,
(15) allyl-di-tert-butylphosphonium tetraphenylborate,
(16) tricyclohexylphosphonium tetra-para-tolylborate,
(17) triisopropylphosphonium tetraphenylborate,
(18) tricyclopentylphosphonium tetraphenylborate and
(19) n-butyldicyclohexylphosphonium tetraphenylborate.

Of these, the compounds (1), (3), (16) and (17) are more preferable.

The phosphonium borate compounds (I) are particularly useful in combination with a transition metal, salt thereof, oxide thereof or complex thereof in the carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions wherein a transition metal complex having a phosphine ligand produces catalytic effects, wherein the phosphonium borate compounds in combination with the transition metal, salt thereof, oxide thereof or complex thereof are used in place of the transition metal complex having a phosphine ligand.

<Use>

The phosphonium borate compounds (I) can be used in combination with a transition metal, transition metal salt, transition metal oxide or transition metal complex in the carbon-carbon bond forming reactions such as Suzuki-Miyaura reaction, Kumada reaction, Negishi reaction, Hiyama reaction, Kosugi-Stille reaction, Heck reaction, Endo reaction and α-allylation of carbonyl compounds; carbon-nitrogen bond forming reactions such as Buchwald-Hartwig amination; and carbon-oxygen bond forming reactions such as ether synthesis wherein a transition metal complex having a phosphine ligand produces catalytic effects, wherein the phosphonium borate compounds in combination with the transition metal, transition metal salt, transition metal oxide or transition metal complex are used in place of the transition metal complex having a phosphine ligand.

The transition metals include, but are not limited to, manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum.

The transition metal salts include fluorides, chlorides, bromides, iodides, sulfates, nitrates, nitrites, carbonates, borates, ammonium salts, sodium salts, potassium salts, acetates, trifluoroacetates, acetylacetone salts, hydride salts, sulfides and cyanides of manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum. Hydrates of these transition metal salts are also employable. Specific examples include, but are not limited to, manganese (II) chloride, iron (II) chloride, iron (III) chloride, cobalt (II) chloride, nickel (II) chloride, ruthenium (III) chloride, rhodium (III) chloride, palladium (II) chloride, palladium (II) bromide, manganese (II) acetate, manganese (III) acetate, iron (II) acetate, cobalt (II) acetate, nickel (II) acetate, rhodium (II) acetate dimer, palladium (II) acetate, manganese (II) acetylacetonate, manganese (III) acetylacetonate, iron (II) acetylacetonate, iron (III) acetylacetonate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, nickel (II) acetylacetonate, ruthenium (III) acetylacetonate, rhodium (III) acetylacetonate, palladium (II) acetylacetonate, platinum (II) acetylacetonate and sodium (IV) chloroplatinate hexahydrate.

The transition metal oxides include oxides of manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum. Hydrates of these transition metal oxides are also employable. Specific examples include, but are not limited to, manganese (II) oxide, iron (III) oxide, cobalt (II) oxide, nickel (II) oxide, ruthenium (IV) oxide, rhodium (III) oxide, palladium (II) oxide and platinum (IV) oxide.

The transition metal complexes include benzonitrile complexes, acetonitrile complexes, triphenylphosphine complexes, ethylene complexes, allyl complexes, butadiene complexes, cyclopentadiene complexes, cyclooctadiene complexes, cyclooctatetraene complexes, carbonyl complexes, dibenzylideneacetone complexes, amine complexes, ethylenediamine complexes, pyridine complexes and disiloxane complexes of manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum. Hydrates of these transition metal complexes are also employable. Specific examples include, but are not limited to, decacarbonylmanganese (0), bis(cyclooctatetraene)iron (0), bis (cyclopentadienyl)cobalt (0), bis(cyclooctadiene)nickel (0), bis (cyclopentadienyl) ruthenium (0), tetrarhodiumdodecacarbonyl (0), tris(dibenzylideneacetone)dipalladium (0), bis(benzonitrile)dichloropalladium (II), allylpalladium chloride dimer and divinyltetramethyldisiloxane platinum (0).

Tables 1-1 to 4-2 below show specific examples of the phosphines of Formula (II) that are used as starting compounds in the embodiment 2 of the first production process and the embodiment 2 of the second production process for producing a phosphonium borate compound according to the present invention. Tables 5 to 10 below show specific examples of the tetraarylborate compounds of Formula (IV). Tables 11-1 to 18-3 below show specific examples of the novel phosphonium borate compounds (I) according to the present invention.

Specific examples of the phosphines (II) represented by Formula (II):
(R¹)(R²)(R³)P (II)
include, but are not limited to, the following compounds.

TABLE 1 Table 1-1 R¹ R² R³ tert-butyl tert-butyl hydrogen tert-butyl tert-butyl methyl tert-butyl tert-butyl ethyl tert-butyl tert-butyl n-propyl tert-butyl tert-butyl n-butyl tert-butyl tert-butyl isobutyl tert-butyl tert-butyl n-pentyl tert-butyl tert-butyl isopentyl tert-butyl tert-butyl n-hexyl tert-butyl tert-butyl 2-methyl-1-pentyl tert-butyl tert-butyl 2,2-diethyl-1-ethyl tert-butyl tert-butyl n-heptyl tert-butyl tert-butyl n-octyl tert-butyl tert-butyl isopropyl tert-butyl tert-butyl sec-butyl tert-butyl tert-butyl 2-pentyl tert-butyl tert-butyl 3-pentyl tert-butyl tert-butyl 2-hexyl tert-butyl tert-butyl 3-hexyl tert-butyl tert-butyl tert-butyl tert-butyl tert-butyl tert-amyl tert-butyl tert-butyl 1,1-dimethylbutyl tert-butyl tert-butyl 3-methyl-3-pentyl tert-butyl tert-butyl 1,1,2-trimethylpropyl tert-butyl tert-butyl 1-adamantyl tert-butyl tert-butyl 2-methyl-1-adamantyl tert-butyl tert-butyl cyclopropyl tert-butyl tert-butyl cyclopentyl tert-butyl tert-butyl cyclohexyl tert-butyl tert-butyl 1-methylcyclohexyl tert-butyl tert-butyl 2-methylcyclohexyl tert-butyl tert-butyl 2-adamantyl tert-butyl tert-butyl 1-methyl-2-adamantyl tert-butyl tert-butyl 2-methyl-2-adamantyl tert-butyl tert-butyl phenyl tert-butyl tert-butyl ortho-tolyl tert-butyl tert-butyl meta-tolyl tert-butyl tert-butyl para-tolyl tert-butyl tert-butyl 2,3-xylyl tert-butyl tert-butyl 2,4-xylyl tert-butyl tert-butyl 2,5-xylyl tert-butyl tert-butyl 2,6-xylyl tert-butyl tert-butyl 3,4-xylyl tert-butyl tert-butyl 3,5-xylyl tert-butyl tert-butyl mesityl

TABLE 2 Table 1-2 R¹ R² R³ tert-butyl tert-butyl 2-tert-butylphenyl tert-butyl tert-butyl 3-tert-butylphenyl tert-butyl tert-butyl 4-tert-butylphenyl tert-butyl tert-butyl 2-ethenylphenyl tert-butyl tert-butyl 3-ethenylphenyl tert-butyl tert-butyl 4-ethenylphenyl tert-butyl tert-butyl 2-biphenylyl tert-butyl tert-butyl 3-biphenylyl tert-butyl tert-butyl 4-biphenylyl tert-butyl tert-butyl 1-naphthyl tert-butyl tert-butyl 2-naphthyl tert-butyl tert-butyl 1,1′-binaphthalene-2-yl tert-butyl tert-butyl 2-methoxyphenyl tert-butyl tert-butyl 3-methoxyphenyl tert-butyl tert-butyl 4-methoxyphenyl tert-butyl tert-butyl 2-tert-butoxyphenyl tert-butyl tert-butyl 3-tert-butoxyphenyl tert-butyl tert-butyl 4-tert-butoxyphenyl tert-butyl tert-butyl 2-dimethylaminophenyl tert-butyl tert-butyl 3-dimethylaminophenyl tert-butyl tert-butyl 4-dimethylaminophenyl tert-butyl tert-butyl 2′-dimethylamino-2-biphenylyl tert-butyl tert-butyl 8-dimethylamino-1-naphthyl tert-butyl tert-butyl 2′-dimethylamino-1,1′-binaphthalene-2-yl tert-butyl tert-butyl benzyl tert-butyl tert-butyl 1-phenylethyl tert-butyl tert-butyl 2-phenylethyl tert-butyl tert-butyl 2-ethenylbenzyl tert-butyl tert-butyl 3-ethenylbenzyl tert-butyl tert-butyl 4-ethenylbenzyl tert-butyl tert-butyl 4-(2-ethenylphenyl)butyl tert-butyl tert-butyl 4-(3-ethenylphenyl)butyl tert-butyl tert-butyl 4-(4-ethenylphenyl)butyl tert-butyl tert-butyl vinyl tert-butyl tert-butyl methallyl tert-butyl tert-butyl 1-octenyl tert-butyl tert-butyl ethynyl tert-butyl tert-butyl 1-propynyl tert-butyl tert-butyl 1-octynyl tert-butyl tert-butyl allyl tert-butyl tert-butyl 2-octenyl isopropyl isopropyl isopropyl n-butyl cyclohexyl cyclohexyl cyclopentyl cyclopentyl cyclopentyl cyclohexyl cyclohexyl cyclohexyl

TABLE 3 Table 2-1 R¹ R² R³ tert-amyl tert-amyl hydrogen tert-amyl tert-amyl methyl tert-amyl tert-amyl ethyl tert-amyl tert-amyl n-propyl tert-amyl tert-amyl n-butyl tert-amyl tert-amyl isobutyl tert-amyl tert-amyl n-pentyl tert-amyl tert-amyl isopentyl tert-amyl tert-amyl n-hexyl tert-amyl tert-amyl 2-methyl-1-pentyl tert-amyl tert-amyl 2,2-diethyl-1-ethyl tert-amyl tert-amyl n-heptyl tert-amyl tert-amyl n-octyl tert-amyl tert-amyl isopropyl tert-amyl tert-amyl sec-butyl tert-amyl tert-amyl 2-pentyl tert-amyl tert-amyl 3-pentyl tert-amyl tert-amyl 2-hexyl tert-amyl tert-amyl 3-hexyl tert-amyl tert-amyl tert-butyl tert-amyl tert-amyl tert-amyl tert-amyl tert-amyl 1,1-dimethylbutyl tert-amyl tert-amyl 3-methyl-3-pentyl tert-amyl tert-amyl 1,1,2-trimethylpropyl tert-amyl tert-amyl 1-adamantyl tert-amyl tert-amyl 2-methyl-1-adamantyl tert-amyl tert-amyl cyclopropyl tert-amyl tert-amyl cyclopentyl tert-amyl tert-amyl cyclohexyl tert-amyl tert-amyl 1-methylcyclohexyl tert-amyl tert-amyl 2-methylcyclohexyl tert-amyl tert-amyl 2-adamantyl tert-amyl tert-amyl 1-methyl-2-adamantyl tert-amyl tert-amyl 2-methyl-2-adamantyl tert-amyl tert-amyl phenyl tert-amyl tert-amyl ortho-tolyl tert-amyl tert-amyl meta-tolyl tert-amyl tert-amyl para-tolyl tert-amyl tert-amyl 2,3-xylyl tert-amyl tert-amyl 2,4-xylyl tert-amyl tert-amyl 2,5-xylyl tert-amyl tert-amyl 2,6-xylyl tert-amyl tert-amyl 3,4-xylyl

TABLE 4 Table 2-2 R¹ R² R³ tert-amyl tert-amyl 3,5-xylyl tert-amyl tert-amyl mesityl tert-amyl tert-amyl 2-tert-butylphenyl tert-amyl tert-amyl 3-tert-butylphenyl tert-amyl tert-amyl 4-tert-butylphenyl tert-amyl tert-amyl 2-ethenylphenyl tert-amyl tert-amyl 3-ethenylphenyl tert-amyl tert-amyl 4-ethenylphenyl tert-amyl tert-amyl 2-biphenylyl tert-amyl tert-amyl 3-biphenylyl tert-amyl tert-amyl 4-biphenylyl tert-amyl tert-amyl 1-naphthyl tert-amyl tert-amyl 2-naphthyl tert-amyl tert-amyl 1,1′-binaphthalene-2-yl tert-amyl tert-amyl 2-methoxyphenyl tert-amyl tert-amyl 3-methoxyphenyl tert-amyl tert-amyl 4-methoxyphenyl tert-amyl tert-amyl 2-tert-butoxyphenyl tert-amyl tert-amyl 3-tert-butoxyphenyl tert-amyl tert-amyl 4-tert-butoxyphenyl tert-amyl tert-amyl 2-dimethylaminophenyl tert-amyl tert-amyl 3-dimethylaminophenyl tert-amyl tert-amyl 4-dimethylaminophenyl tert-amyl tert-amyl 2′-dimethylamino-2-biphenylyl tert-amyl tert-amyl 8-dimethylamino-1-naphthyl tert-amyl tert-amyl 2′-dimethylamino-1,1′-binaphthalene-2-yl tert-amyl tert-amyl benzyl tert-amyl tert-amyl 1-phenylethyl tert-amyl tert-amyl 2-phenylethyl tert-amyl tert-amyl 2-ethenylbenzyl tert-amyl tert-amyl 3-ethenylbenzyl tert-amyl tert-amyl 4-ethenylbenzyl tert-amyl tert-amyl 4-(2-ethenylphenyl)butyl tert-amyl tert-amyl 4-(3-ethenylphenyl)butyl tert-amyl tert-amyl 4-(4-ethenylphenyl)butyl tert-amyl tert-amyl vinyl tert-amyl tert-amyl methallyl tert-amyl tert-amyl 1-octenyl tert-amyl tert-amyl ethynyl tert-amyl tert-amyl 1-propynyl tert-amyl tert-amyl 1-octynyl tert-amyl tert-amyl allyl tert-amyl tert-amyl 2-octenyl

TABLE 5 Table 3-1 R¹ R² R³ 1-adamantyl 1-adamantyl hydrogen 1-adamantyl 1-adamantyl methyl 1-adamantyl 1-adamantyl ethyl 1-adamantyl 1-adamantyl n-propyl 1-adamantyl 1-adamantyl n-butyl 1-adamantyl 1-adamantyl isobutyl 1-adamantyl 1-adamantyl n-pentyl 1-adamantyl 1-adamantyl isopentyl 1-adamantyl 1-adamantyl n-hexyl 1-adamantyl 1-adamantyl 2-methyl-1-pentyl 1-adamantyl 1-adamantyl 2,2-diethyl-1-ethyl 1-adamantyl 1-adamantyl n-heptyl 1-adamantyl 1-adamantyl n-octyl 1-adamantyl 1-adamantyl isopropyl 1-adamantyl 1-adamantyl sec-butyl 1-adamantyl 1-adamantyl 2-pentyl 1-adamantyl 1-adamantyl 3-pentyl 1-adamantyl 1-adamantyl 2-hexyl 1-adamantyl 1-adamantyl 3-hexyl 1-adamantyl 1-adamantyl tert-butyl 1-adamantyl 1-adamantyl tert-amyl 1-adamantyl 1-adamantyl 1,1-dimethylbutyl 1-adamantyl 1-adamantyl 3-methyl-3-pentyl 1-adamantyl 1-adamantyl 1,1,2-trimethylpropyl 1-adamantyl 1-adamantyl 1-adamantyl 1-adamantyl 1-adamantyl 2-methyl-1-adamantyl 1-adamantyl 1-adamantyl cyclopropyl 1-adamantyl 1-adamantyl cyclopentyl 1-adamantyl 1-adamantyl cyclohexyl 1-adamantyl 1-adamantyl 1-methylcyclohexyl 1-adamantyl 1-adamantyl 2-methylcyclohexyl 1-adamantyl 1-adamantyl 2-adamantyl 1-adamantyl 1-adamantyl 1-methyl-2-adamantyl 1-adamantyl 1-adamantyl 2-methyl-2-adamantyl 1-adamantyl 1-adamantyl phenyl 1-adamantyl 1-adamantyl ortho-tolyl 1-adamantyl 1-adamantyl meta-tolyl 1-adamantyl 1-adamantyl para-tolyl 1-adamantyl 1-adamantyl 2,3-xylyl 1-adamantyl 1-adamantyl 2,4-xylyl 1-adamantyl 1-adamantyl 2,5-xylyl 1-adamantyl 1-adamantyl 2,6-xylyl 1-adamantyl 1-adamantyl 3,4-xylyl 1-adamantyl 1-adamantyl 3,5-xylyl 1-adamantyl 1-adamantyl mesityl

TABLE 6 Table 3-2 R¹ R² R³ 1-adamantyl 1-adamantyl 2-tert-butylphenyl 1-adamantyl 1-adamantyl 3-tert-butylphenyl 1-adamantyl 1-adamantyl 4-tert-butylphenyl 1-adamantyl 1-adamantyl 2-ethenylphenyl 1-adamantyl 1-adamantyl 3-ethenylphenyl 1-adamantyl 1-adamantyl 4-ethenylphenyl 1-adamantyl 1-adamantyl 2-biphenylyl 1-adamantyl 1-adamantyl 3-biphenylyl 1-adamantyl 1-adamantyl 4-biphenylyl 1-adamantyl 1-adamantyl 1-naphthyl 1-adamantyl 1-adamantyl 2-naphthyl 1-adamantyl 1-adamantyl 1,1′-binaphthalene-2-yl 1-adamantyl 1-adamantyl 2-methoxyphenyl 1-adamantyl 1-adamantyl 3-methoxyphenyl 1-adamantyl 1-adamantyl 4-methoxyphenyl 1-adamantyl 1-adamantyl 2-tert-butoxyphenyl 1-adamantyl 1-adamantyl 3-tert-butoxyphenyl 1-adamantyl 1-adamantyl 4-tert-butoxyphenyl 1-adamantyl 1-adamantyl 2-dimethylaimnophenyl 1-adamantyl 1-adamantyl 3-dimethylaminophenyl 1-adamantyl 1-adamantyl 4-dimethylaminophenyl 1-adamantyl 1-adamantyl 2′-dimethylamino-2-biphenylyl 1-adamantyl 1-adamantyl 8-dimethylamino-1-naphthyl 1-adamantyl 1-adamantyl 2′-dimethylamino-1,1′-binaphthalene-2-yl 1-adamantyl 1-adamantyl benzyl 1-adamantyl 1-adamantyl 1-phenylethyl 1-adamantyl 1-adamantyl 2-phenylethyl 1-adamantyl 1-adamantyl 2-ethenylbenzyl 1-adamantyl 1-adamantyl 3-ethenylbenzyl 1-adamantyl 1-adamantyl 4-ethenylbenzyl 1-adamantyl 1-adamantyl 4-(2-ethenylphenyl)butyl 1-adamantyl 1-adamantyl 4-(3-ethenylphenyl)butyl 1-adamantyl 1-adamantyl 4-(4-ethenylphenyl)butyl 1-adamantyl 1-adamantyl vinyl 1-adamantyl 1-adamantyl methallyl 1-adamantyl 1-adamantyl 1-octenyl 1-adamantyl 1-adamantyl ethynyl 1-adamantyl 1-adamantyl 1-propynyl 1-adamantyl 1-adamantyl 1-octynyl 1-adamantyl 1-adamantyl allyl 1-adamantyl 1-adamantyl 2-octenyl

TABLE 7 Table 4-1 R¹ R² R³ 2-adamantyl 2-adamantyl hydrogen 2-adamantyl 2-adamantyl methyl 2-adamantyl 2-adamantyl ethyl 2-adamantyl 2-adamantyl n-propyl 2-adamantyl 2-adamantyl n-butyl 2-adamantyl 2-adamantyl isobutyl 2-adamantyl 2-adamantyl n-pentyl 2-adamantyl 2-adamantyl isopentyl 2-adamantyl 2-adamantyl n-hexyl 2-adamantyl 2-adamantyl 2-methyl-1-pentyl 2-adamantyl 2-adamantyl 2,2-diethyl-1-ethyl 2-adamantyl 2-adamantyl n-heptyl 2-adamantyl 2-adamantyl n-octyl 2-adamantyl 2-adamantyl isopropyl 2-adamantyl 2-adamantyl sec-butyl 2-adamantyl 2-adamantyl 2-pentyl 2-adamantyl 2-adamantyl 3-pentyl 2-adamantyl 2-adamantyl 2-hexyl 2-adamantyl 2-adamantyl 3-hexyl 2-adamantyl 2-adamantyl tert-butyl 2-adamantyl 2-adamantyl tert-amyl 2-adamantyl 2-adamantyl 1,1-dimethylbutyl 2-adamantyl 2-adamantyl 3-methyl-3-pentyl 2-adamantyl 2-adamantyl 1,1,2-trimethylpropyl 2-adamantyl 2-adamantyl 1-adamantyl 2-adamantyl 2-adamantyl 2-methyl-1-adamantyl 2-adamantyl 2-adamantyl cyclopropyl 2-adamantyl 2-adamantyl cyclopentyl 2-adamantyl 2-adamantyl cyclohexyl 2-adamantyl 2-adamantyl 1-methylcyclohexyl 2-adamantyl 2-adamantyl 2-methylcyclohexyl 2-adamantyl 2-adamantyl 2-adamantyl 2-adamantyl 2-adamantyl 1-methyl-2-adamantyl 2-adamantyl 2-adamantyl 2-methyl-2-adamantyl 2-adamantyl 2-adamantyl phenyl 2-adamantyl 2-adamantyl ortho-tolyl 2-adamantyl 2-adamantyl meta-tolyl 2-adamantyl 2-adamantyl para-tolyl 2-adamantyl 2-adamantyl 2,3-xylyl 2-adamantyl 2-adamantyl 2,4-xylyl 2-adamantyl 2-adamantyl 2,5-xylyl 2-adamantyl 2-adamantyl 2,6-xylyl 2-adamantyl 2-adamantyl 3,4-xylyl 2-adamantyl 2-adamantyl 3,5-xylyl 2-adamantyl 2-adamantyl mesityl

TABLE 8 Table 4-2 R¹ R² R³ 2-adamantyl 2-adamantyl 2-tert-butylphenyl 2-adamantyl 2-adamantyl 3-tert-butylphenyl 2-adamantyl 2-adamantyl 4-tert-butylphenyl 2-adamantyl 2-adamantyl 2-ethenylphenyl 2-adamantyl 2-adamantyl 3-ethenylphenyl 2-adamantyl 2-adamantyl 4-ethenylphenyl 2-adamantyl 2-adamantyl 2-biphenylyl 2-adamantyl 2-adamantyl 3-biphenylyl 2-adamantyl 2-adamantyl 4-biphenylyl 2-adamantyl 2-adamantyl 1-naphthyl 2-adamantyl 2-adamantyl 2-naphthyl 2-adamantyl 2-adamantyl 1,1′-binaphthalene-2-yl 2-adamantyl 2-adamantyl 2-methoxyphenyl 2-adamantyl 2-adamantyl 3-methoxyphenyl 2-adamantyl 2-adamantyl 4-methoxyphenyl 2-adamantyl 2-adamantyl 2-tert-butoxyphenyl 2-adamantyl 2-adamantyl 3-tert-butoxyphenyl 2-adamantyl 2-adamantyl 4-tert-butoxyphenyl 2-adamantyl 2-adamantyl 2-dimethylaminophenyl 2-adamantyl 2-adamantyl 3-dimethylaminophenyl 2-adamantyl 2-adamantyl 4-dimethylaminophenyl 2-adamantyl 2-adamantyl 2′-dimethylamino-2-biphenylyl 2-adamantyl 2-adamantyl 8-dimethylamino-1-naphthyl 2-adamantyl 2-adamantyl 2′-dimethylamino-1,1′-binaphthalene-2-yl 2-adamantyl 2-adamantyl benzyl 2-adamantyl 2-adamantyl 1-phenylethyl 2-adamantyl 2-adamantyl 2-phenylethyl 2-adamantyl 2-adamantyl 2-ethenylbenzyl 2-adamantyl 2-adamantyl 3-ethenylbenzyl 2-adamantyl 2-adamantyl 4-ethenylbenzyl 2-adamantyl 2-adamantyl 4-(2-ethenylphenyl)butyl 2-adamantyl 2-adamantyl 4-(3-ethenylphenyl)butyl 2-adamantyl 2-adamantyl 4-(4-ethenylphenyl)butyl 2-adamantyl 2-adamantyl vinyl 2-adamantyl 2-adamantyl methallyl 2-adamantyl 2-adamantyl 1-octenyl 2-adamantyl 2-adamantyl ethynyl 2-adamantyl 2-adamantyl 1-propynyl 2-adamantyl 2-adamantyl 1-octynyl 2-adamantyl 2-adamantyl allyl 2-adamantyl 2-adamantyl 2-octenyl

Tables 5 to 10 below show specific examples of the tetraarylborate compounds of Formula (IV):
M.BAr₄ (IV)
that are used as starting compounds in the embodiment 2 of the first production process and the embodiment 2 of the second production process according to the present invention. The compounds are not limited thereto.

TABLE 9 Table 5 Ar M phenyl lithium ortho-tolyl lithium meta-tolyl lithium para-tolyl lithium 2,3-xylyl lithium 2,4-xylyl lithium 2,5-xylyl lithium 2,6-xylyl lithium 3,4-xylyl lithium 3,5-xylyl lithium mesityl lithium 2-tert-butylphenyl lithium 3-tert-butylphenyl lithium 4-tert-butylphenyl lithium 2-methoxyphenyl lithium 3-methoxyphenyl lithium 4-methoxyphenyl lithium 2-tert-butoxyphenyl lithium 3-tert-butoxyphenyl lithium 4-tert-butoxyphenyl lithium

TABLE 10 Table 6 Ar M phenyl sodium ortho-tolyl sodium meta-tolyl sodium para-tolyl sodium 2,3-xylyl sodium 2,4-xylyl sodium 2,5-xylyl sodium 2,6-xylyl sodium 3,4-xylyl sodium 3,5-xylyl sodium mesityl sodium 2-tert-butylphenyl sodium 3-tert-butylphenyl sodium 4-tert-butylphenyl sodium 2-methoxyphenyl sodium 3-methoxyphenyl sodium 4-methoxyphenyl sodium 2-tert-butoxyphenyl sodium 3-tert-butoxyphenyl sodium 4-tert-butoxyphenyl sodium

TABLE 11 Table 7 Ar M phenyl potassium ortho-tolyl potassium meta-tolyl potassium para-tolyl potassium 2,3-xylyl potassium 2,4-xylyl potassium 2,5-xylyl potassium 2,6-xylyl potassium 3,4-xylyl potassium 3,5-xylyl potassium mesityl potassium 2-tert-butylphenyl potassium 3-tert-butylphenyl potassium 4-tert-butylphenyl potassium 2-methoxyphenyl potassium 3-methoxyphenyl potassium 4-methoxyphenyl potassium 2-tert-butoxyphenyl potassium 3-tert-butoxyphenyl potassium 4-tert-butoxyphenyl potassium

TABLE 12 Table 8 Ar M phenyl magnesium chloride ortho-tolyl magnesium chloride meta-tolyl magnesium chloride para-tolyl magnesium chloride 2,3-xylyl magnesium chloride 2,4-xylyl magnesium chloride 2,5-xylyl magnesium chloride 2,6-xylyl magnesium chloride 3,4-xylyl magnesium chloride 3,5-xylyl magnesium chloride mesityl magnesium chloride 2-tert-butylphenyl magnesium chloride 3-tert-butylphenyl magnesium chloride 4-tert-butylphenyl magnesium chloride 2-methoxyphenyl magnesium chloride 3-methoxyphenyl magnesium chloride 4-methoxyphenyl magnesium chloride 2-tert-butoxyphenyl magnesium chloride 3-tert-butoxyphenyl magnesium chloride 4-tert-butoxyphenyl magnesium chloride

TABLE 13 Table 9 Ar M phenyl magnesium bromide ortho-tolyl magnesium bromide meta-tolyl magnesium bromide para-tolyl magnesium bromide 2,3-xylyl magnesium bromide 2,4-xylyl magnesium bromide 2,5-xylyl magnesium bromide 2,6-xylyl magnesium bromide 3,4-xylyl magnesium bromide 3,5-xylyl magnesium bromide mesityl magnesium bromide 2-tert-butylphenyl magnesium bromide 3-tert-butylphenyl magnesium bromide 4-tert-butylphenyl magnesium bromide 2-methoxyphenyl magnesium bromide 3-methoxyphenyl magnesium bromide 4-methoxyphenyl magnesium bromide 2-tert-butoxyphenyl magnesium bromide 3-tert-butoxyphenyl magnesium bromide 4-tert-butoxyphenyl magnesium bromide

TABLE 14 Table 10 Ar M phenyl calcium chloride ortho-tolyl calcium chloride meta-tolyl calcium chloride para-tolyl calcium chloride 2,3-xylyl calcium chloride 2,4-xylyl calcium chloride 2,5-xylyl calcium chloride 2,6-xylyl calcium chloride 3,4-xylyl calcium chloride 3,5-xylyl calcium chloride mesityl calcium chloride 2-tert-butylphenyl calcium chloride 3-tert-butylphenyl calcium chloride 4-tert-butylphenyl calcium chloride 2-methoxyphenyl calcium chloride 3-methoxyphenyl calcium chloride 4-methoxyphenyl calcium chloride 2-tert-butoxyphenyl calcium chloride 3-tert-butoxyphenyl calcium chloride 4-tert-butoxyphenyl calcium chloride

Tables 11-1 to 18-3 below show specific examples of the 5 novel phosphonium borate compounds represented by Formula (I):
(R¹)(R²)(R³)PH.BAr₄ (I)
that are produced according to the present invention. The compounds are not limited thereto.

TABLE 15 Table 11-1 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-butyl tert-butyl hydrogen phenyl tert-butyl tert-butyl methyl phenyl 192-196 tert-butyl tert-butyl ethyl phenyl 174-188 tert-butyl tert-butyl n-propyl phenyl tert-butyl tert-butyl n-butyl phenyl 156-162 tert-butyl tert-butyl isobutyl phenyl tert-butyl tert-butyl n-pentyl phenyl tert-butyl tert-butyl isopentyl phenyl tert-butyl tert-butyl n-hexyl phenyl tert-butyl tert-butyl 2-methyl-1-pentyl phenyl tert-butyl tert-butyl 2,2-diethyl-1-ethyl phenyl tert-butyl tert-butyl n-heptyl phenyl tert-butyl tert-butyl n-octyl phenyl 108-113 tert-butyl tert-butyl isopropyl phenyl tert-butyl tert-butyl sec-butyl phenyl 184-187 tert-butyl tert-butyl 2-pentyl phenyl tert-butyl tert-butyl 3-pentyl phenyl tert-butyl tert-butyl 2-hexyl phenyl tert-butyl tert-butyl 3-hexyl phenyl tert-butyl tert-butyl tert-amyl phenyl tert-butyl tert-butyl 1,1-dimethylbutyl phenyl tert-butyl tert-butyl 3-methyl-3-pentyl phenyl tert-butyl tert-butyl 1,1,2-trimethylpropyl phenyl tert-butyl tert-butyl 1-adamantyl phenyl tert-butyl tert-butyl 2-methyl-1-adamantyl phenyl tert-butyl tert-butyl cyclopropyl phenyl tert-butyl tert-butyl cyclopentyl phenyl tert-butyl tert-butyl cyclohexyl phenyl 171-178 tert-butyl tert-butyl 1-methylcyclohexyl phenyl tert-butyl tert-butyl 2-methylcyclohexyl phenyl tert-butyl tert-butyl 2-adamantyl phenyl tert-butyl tert-butyl 1-methyl-2-adamantyl phenyl

TABLE 16 Table 11-2 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-butyl tert-butyl 2-methyl-2-adamantyl phenyl tert-butyl tert-butyl phenyl phenyl 135-140 tert-butyl tert-butyl ortho-tolyl phenyl tert-butyl tert-butyl meta-tolyl phenyl tert-butyl tert-butyl para-tolyl phenyl tert-butyl tert-butyl 2,3-xylyl phenyl tert-butyl tert-butyl 2,4-xylyl phenyl tert-butyl tert-butyl 2,5-xylyl phenyl tert-butyl tert-butyl 2,6-xylyl phenyl tert-butyl tert-butyl 3,4-xylyl phenyl tert-butyl tert-butyl 3,5-xylyl phenyl tert-butyl tert-butyl mesityl phenyl tert-butyl tert-butyl 2-tert-butylphenyl phenyl tert-butyl tert-butyl 3-tert-butylphenyl phenyl tert-butyl tert-butyl 4-tert-butylphenyl phenyl tert-butyl tert-butyl 2-ethenylphenyl phenyl tert-butyl tert-butyl 3-ethenylphenyl phenyl tert-butyl tert-butyl 4-ethenylphenyl phenyl tert-butyl tert-butyl 2-biphenylyl phenyl 163-174 tert-butyl tert-butyl 3-biphenylyl phenyl tert-butyl tert-butyl 4-biphenylyl phenyl tert-butyl tert-butyl 1-naphthyl phenyl 165-174 tert-butyl tert-butyl 2-naphthyl phenyl tert-butyl tert-butyl 1,1′-binaphthalene-2-yl phenyl tert-butyl tert-butyl 2-methoxyphenyl phenyl tert-butyl tert-butyl 3-methoxyphenyl phenyl tert-butyl tert-butyl 4-methoxyphenyl phenyl tert-butyl tert-butyl 2-tert-butoxyphenyl phenyl tert-butyl tert-butyl 3-tert-butoxyphenyl phenyl tert-butyl tert-butyl 4-tert-butoxyphenyl phenyl

TABLE 17 Table 11-3 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-butyl tert-butyl 2-dimethyl- phenyl aminophenyl tert-butyl tert-butyl 3-dimethyl- phenyl aminophenyl tert-butyl tert-butyl 4-dimethyl- phenyl aminophenyl tert-butyl tert-butyl 2′-dimethylamino-2- phenyl biphenylyl tert-butyl tert-butyl 8-dimethylamino-1- phenyl naphthyl tert-butyl tert-butyl 2′-dimethylamino-1,1′- phenyl binaphthalene-2-yl tert-butyl tert-butyl benzyl phenyl 149-158 tert-butyl tert-butyl 1-phenylethyl phenyl tert-butyl tert-butyl 2-phenylethyl phenyl tert-butyl tert-butyl 2-ethenylbenzyl phenyl tert-butyl tert-butyl 3-ethenylbenzyl phenyl tert-butyl tert-butyl 4-ethenylbenzyl phenyl 122-132 tert-butyl tert-butyl 4-(2- phenyl ethenylphenyl)butyl tert-butyl tert-butyl 4-(3- phenyl ethenylphenyl)butyl tert-butyl tert-butyl 4-(4- phenyl ethenylphenyl)butyl tert-butyl tert-butyl vinyl phenyl 253-261 tert-butyl tert-butyl methallyl phenyl tert-butyl tert-butyl 1-octenyl phenyl tert-butyl tert-butyl ethynyl phenyl tert-butyl tert-butyl 1-propynyl phenyl tert-butyl tert-butyl 1-octynyl phenyl tert-butyl tert-butyl allyl phenyl 148-160 tert-butyl tert-butyl 2-octenyl phenyl isopropyl isopropyl isopropyl phenyl 194-214 n-butyl cyclohexyl cyclohexyl phenyl 175-180 cyclopentyl cyclopentyl cyclopentyl phenyl 178-187

TABLE 18 Table 12-1 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-amyl tert-amyl hydrogen phenyl tert-amyl tert-amyl methyl phenyl tert-amyl tert-amyl ethyl phenyl tert-amyl tert-amyl n-propyl phenyl tert-amyl tert-amyl n-butyl phenyl tert-amyl tert-amyl isobutyl phenyl tert-amyl tert-amyl n-pentyl phenyl tert-amyl tert-amyl isopentyl phenyl tert-amyl tert-amyl n-hexyl phenyl tert-amyl tert-amyl 2-methyl-1-pentyl phenyl tert-amyl tert-amyl 2,2-diethyl-1-ethyl phenyl tert-amyl tert-amyl n-heptyl phenyl tert-amyl tert-amyl n-octyl phenyl tert-amyl tert-amyl isopropyl phenyl tert-amyl tert-amyl sec-butyl phenyl tert-amyl tert-amyl 2-pentyl phenyl tert-amyl tert-amyl 3-pentyl phenyl tert-amyl tert-amyl 2-hexyl phenyl tert-amyl tert-amyl 3-hexyl phenyl tert-amyl tert-amyl tert-butyl phenyl tert-amyl tert-amyl tert-amyl phenyl tert-amyl tert-amyl 1,1-dimethylbutyl phenyl tert-amyl tert-amyl 3-methyl-3-pentyl phenyl tert-amyl tert-amyl 1,1,2-trimethylpropyl phenyl tert-amyl tert-amyl 1-adamantyl phenyl tert-amyl tert-amyl 2-methyl-1-adamantyl phenyl tert-amyl tert-amyl cyclopropyl phenyl tert-amyl tert-amyl cyclopentyl phenyl tert-amyl tert-amyl cyclohexyl phenyl tert-amyl tert-amyl 1-methylcyclohexyl phenyl tert-amyl tert-amyl 2-methylcyclohexyl phenyl tert-amyl tert-amyl 2-adamantyl phenyl tert-amyl tert-amyl 1-methyl-2-adamantyl phenyl tert-amyl tert-amyl 2-methyl-2-adamantyl phenyl

TABLE 19 Table 12-2 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-amyl tert-amyl phenyl phenyl tert-amyl tert-amyl ortho-tolyl phenyl tert-amyl tert-amyl meta-tolyl phenyl tert-amyl tert-amyl para-tolyl phenyl tert-amyl tert-amyl 2,3-xylyl phenyl tert-amyl tert-amyl 2,4-xylyl phenyl tert-amyl tert-amyl 2,5-xylyl phenyl tert-amyl tert-amyl 2,6-xylyl phenyl tert-amyl tert-amyl 3,4-xylyl phenyl tert-amyl tert-amyl 3,5-xylyl phenyl tert-amyl tert-amyl mesityl phenyl tert-amyl tert-amyl 2-tert-butylphenyl phenyl tert-amyl tert-amyl 3-tert-butylphenyl phenyl tert-amyl tert-amyl 4-tert-butylphenyl phenyl tert-amyl tert-amyl 2-ethenylphenyl phenyl tert-amyl tert-amyl 3-ethenylphenyl phenyl tert-amyl tert-amyl 4-ethenylphenyl phenyl tert-amyl tert-amyl 2-biphenylyl phenyl tert-amyl tert-amyl 3-biphenylyl phenyl tert-amyl tert-amyl 4-biphenylyl phenyl tert-amyl tert-amyl 1-naphthyl phenyl tert-amyl tert-amyl 2-naphthyl phenyl tert-amyl tert-amyl 1,1′-binaphthalene-2-yl phenyl tert-amyl tert-amyl 2-methoxyphenyl phenyl tert-amyl tert-amyl 3-methoxyphenyl phenyl tert-amyl tert-amyl 4-methoxyphenyl phenyl tert-amyl tert-amyl 2-tert-butoxyphenyl phenyl tert-amyl tert-amyl 3-tert-butoxyphenyl phenyl tert-amyl tert-amyl 4-tert-butoxyphenyl phenyl tert-amyl tert-amyl 2- phenyl dimethylaminophenyl

TABLE 20 Table 12-3 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-amyl tert-amyl 3-dimethylaminophenyl phenyl tert-amyl tert-amyl 4-dimethylaminophenyl phenyl tert-amyl tert-amyl 2′-dimethylamino-2- phenyl biphenylyl tert-amyl tert-amyl 8-dimethylamino-1- phenyl naphthyl tert-amyl tert-amyl 2′-dimethylamino-1,1′- phenyl binaphthalene-2-yl tert-amyl tert-amyl benzyl phenyl tert-amyl tert-amyl 1-phenylethyl phenyl tert-amyl tert-amyl 2-phenylethyl phenyl tert-amyl tert-amyl 2-ethenylbenzyl phenyl tert-amyl tert-amyl 3-ethenylbenzyl phenyl tert-amyl tert-amyl 4-ethenylbenzyl phenyl tert-amyl tert-amyl 4-(2-ethenylphenyl)butyl phenyl tert-amyl tert-amyl 4-(3-ethenylphenyl)butyl phenyl tert-amyl tert-amyl 4-(4-ethenylphenyl)butyl phenyl tert-amyl tert-amyl vinyl phenyl tert-amyl tert-amyl methallyl phenyl tert-amyl tert-amyl 1-octenyl phenyl tert-amyl tert-amyl ethynyl phenyl tert-amyl tert-amyl 1-propynyl phenyl tert-amyl tert-amyl 1-octynyl phenyl tert-amyl tert-amyl allyl phenyl tert-amyl tert-amyl 2-octenyl phenyl

TABLE 21 Table 13-1 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 1-adamantyl 1-adamantyl hydrogen phenyl 1-adamantyl 1-adamantyl methyl phenyl 1-adamantyl 1-adamantyl ethyl phenyl 1-adamantyl 1-adamantyl n-propyl phenyl 1-adamantyl 1-adamantyl n-butyl phenyl 1-adamantyl 1-adamantyl isobutyl phenyl 1-adamantyl 1-adamantyl n-pentyl phenyl 1-adamantyl 1-adamantyl isopentyl phenyl 1-adamantyl 1-adamantyl n-hexyl phenyl 1-adamantyl 1-adamantyl 2-methyl-1-pentyl phenyl 1-adamantyl 1-adamantyl 2,2-diethyl-1-ethyl phenyl 1-adamantyl 1-adamantyl n-heptyl phenyl 1-adamantyl 1-adamantyl n-octyl phenyl 1-adamantyl 1-adamantyl isopropyl phenyl 1-adamantyl 1-adamantyl sec-butyl phenyl 1-adamantyl 1-adamantyl 2-pentyl phenyl 1-adamantyl 1-adamantyl 3-pentyl phenyl 1-adamantyl 1-adamantyl 2-hexyl phenyl 1-adamantyl 1-adamantyl 3-hexyl phenyl 1-adamantyl 1-adamantyl tert-butyl phenyl 1-adamantyl 1-adamantyl tert-amyl phenyl 1-adamantyl 1-adamantyl 1,1-dimethylbutyl phenyl 1-adamantyl 1-adamantyl 3-methyl-3-pentyl phenyl 1-adamantyl 1-adamantyl 1,1,2-trimethylpropyl phenyl 1-adamantyl 1-adamantyl 1-adamantyl phenyl 1-adamantyl 1-adamantyl 2-methyl-1-adamantyl phenyl 1-adamantyl 1-adamantyl cyclopropyl phenyl 1-adamantyl 1-adamantyl cyclopentyl phenyl 1-adamantyl 1-adamantyl cyclohexyl phenyl 1-adamantyl 1-adamantyl 1-methylcyclohexyl phenyl 1-adamantyl 1-adamantyl 2-methylcyclohexyl phenyl 1-adamantyl 1-adamantyl 2-adamantyl phenyl 1-adamantyl 1-adamantyl 1-methyl-2-adamantyl phenyl

TABLE 22 Table 13-2 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 1-adamantyl 1-adamantyl 2-methyl-2-adamantyl phenyl 1-adamantyl 1-adamantyl phenyl phenyl 1-adamantyl 1-adamantyl ortho-tolyl phenyl 1-adamantyl 1-adamantyl meta-tolyl phenyl 1-adamantyl 1-adamantyl para-tolyl phenyl 1-adamantyl 1-adamantyl 2,3-xylyl phenyl 1-adamantyl 1-adamantyl 2,4-xylyl phenyl 1-adamantyl 1-adamantyl 2,5-xylyl phenyl 1-adamantyl 1-adamantyl 2,6-xylyl phenyl 1-adamantyl 1-adamantyl 3,4-xylyl phenyl 1-adamantyl 1-adamantyl 3,5-xylyl phenyl 1-adamantyl 1-adamantyl mesityl phenyl 1-adamantyl 1-adamantyl 2-tert-butylphenyl phenyl 1-adamantyl 1-adamantyl 3-tert-butylphenyl phenyl 1-adamantyl 1-adamantyl 4-tert-butylphenyl phenyl 1-adamantyl 1-adamantyl 2-ethenylphenyl phenyl 1-adamantyl 1-adamantyl 3-ethenylphenyl phenyl 1-adamantyl 1-adamantyl 4-ethenylphenyl phenyl 1-adamantyl 1-adamantyl 2-biphenylyl phenyl 1-adamantyl 1-adamantyl 3-biphenylyl phenyl 1-adamantyl 1-adamantyl 4-biphenylyl phenyl 1-adamantyl 1-adamantyl 1-naphthyl phenyl 1-adamantyl 1-adamantyl 2-naphthyl phenyl 1-adamantyl 1-adamantyl 1,1′-binaphthalene-2-yl phenyl 1-adamantyl 1-adamantyl 2-methoxyphenyl phenyl 1-adamantyl 1-adamantyl 3-methoxyphenyl phenyl 1-adamantyl 1-adamantyl 4-methoxyphenyl phenyl 1-adamantyl 1-adamantyl 2-tert-butoxyphenyl phenyl 1-adamantyl 1-adamantyl 3-tert-butoxyphenyl phenyl 1-adamantyl 1-adamantyl 4-tert-butoxyphenyl phenyl

TABLE 23 Table 13-3 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 1-adamantyl 1-adamantyl 2-dimethyl- phenyl aminophenyl 1-adamantyl 1-adamantyl 3-dimethyl- phenyl aminophenyl 1-adamantyl 1-adamantyl 4-dimethyl- phenyl aminophenyl 1-adamantyl 1-adamantyl 2′-dimethylamino-2- phenyl biphenylyl 1-adamantyl 1-adamantyl 8-dimethylamino-1- phenyl naphthyl 1-adamantyl 1-adamantyl 2′-dimethylamino-1,1′- phenyl binaphthalene-2-yl 1-adamantyl 1-adamantyl benzyl phenyl 1-adamantyl 1-adamantyl 1-phenylethyl phenyl 1-adamantyl 1-adamantyl 2-phenylethyl phenyl 1-adamantyl 1-adamantyl 2-ethenylbenzyl phenyl 1-adamantyl 1-adamantyl 3-ethenylbenzyl phenyl 1-adamantyl 1-adamantyl 4-ethenylbenzyl phenyl 1-adamantyl 1-adamantyl 4-(2-ethenyl- phenyl phenyl)butyl 1-adamantyl 1-adamantyl 4-(3-ethenyl- phenyl phenyl)butyl 1-adamantyl 1-adamantyl 4-(4-ethenyl- phenyl phenyl)butyl 1-adamantyl 1-adamantyl vinyl phenyl 1-adamantyl 1-adamantyl methallyl phenyl 1-adamantyl 1-adamantyl 1-octenyl phenyl 1-adamantyl 1-adamantyl ethynyl phenyl 1-adamantyl 1-adamantyl 1-propynyl phenyl 1-adamantyl 1-adamantyl 1-octynyl phenyl 1-adamantyl 1-adamantyl allyl phenyl 1-adamantyl 1-adamantyl 2-octenyl phenyl

TABLE 24 Table 14-1 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 2-adamantyl 2-adamantyl hydrogen phenyl 2-adamantyl 2-adamantyl methyl phenyl 2-adamantyl 2-adamantyl ethyl phenyl 2-adamantyl 2-adamantyl n-propyl phenyl 2-adamantyl 2-adamantyl n-butyl phenyl 2-adamantyl 2-adamantyl isobutyl phenyl 2-adamantyl 2-adamantyl n-pentyl phenyl 2-adamantyl 2-adamantyl isopentyl phenyl 2-adamantyl 2-adamantyl n-hexyl phenyl 2-adamantyl 2-adamantyl 2-methyl-1-pentyl phenyl 2-adamantyl 2-adamantyl 2,2-diethyl-1-ethyl phenyl 2-adamantyl 2-adamantyl n-heptyl phenyl 2-adamantyl 2-adamantyl n-octyl phenyl 2-adamantyl 2-adamantyl isopropyl phenyl 2-adamantyl 2-adamantyl sec-butyl phenyl 2-adamantyl 2-adamantyl 2-pentyl phenyl 2-adamantyl 2-adamantyl 3-pentyl phenyl 2-adamantyl 2-adamantyl 2-hexyl phenyl 2-adamantyl 2-adamantyl 3-hexyl phenyl 2-adamantyl 2-adamantyl tert-butyl phenyl 2-adamantyl 2-adamantyl tert-amyl phenyl 2-adamantyl 2-adamantyl 1,1-dimethylbutyl phenyl 2-adamantyl 2-adamantyl 3-methyl-3-pentyl phenyl 2-adamantyl 2-adamantyl 1,1,2-trimethylpropyl phenyl 2-adamantyl 2-adamantyl 1-adamantyl phenyl 2-adamantyl 2-adamantyl 2-methyl-1-adamantyl phenyl 2-adamantyl 2-adamantyl cyclopropyl phenyl 2-adamantyl 2-adamantyl cyclopentyl phenyl 2-adamantyl 2-adamantyl cyclohexyl phenyl 2-adamantyl 2-adamantyl 1-methylcyclohexyl phenyl 2-adamantyl 2-adamantyl 2-methylcyclohexyl phenyl 2-adamantyl 2-adamantyl 2-adamantyl phenyl 2-adamantyl 2-adamantyl 1-methyl-2-adamantyl phenyl 2-adamantyl 2-adamantyl 2-methyl-2-adamantyl phenyl 2-adamantyl 2-adamantyl phenyl phenyl

TABLE 25 Table 14-2 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 2-adamantyl 2-adamantyl ortho-tolyl phenyl 2-adamantyl 2-adamantyl meta-tolyl phenyl 2-adamantyl 2-adamantyl para-tolyl phenyl 2-adamantyl 2-adamantyl 2,3-xylyl phenyl 2-adamantyl 2-adamantyl 2,4-xylyl phenyl 2-adamantyl 2-adamantyl 2,5-xylyl phenyl 2-adamantyl 2-adamantyl 2,6-xylyl phenyl 2-adamantyl 2-adamantyl 3,4-xylyl phenyl 2-adamantyl 2-adamantyl 3,5-xylyl phenyl 2-adamantyl 2-adamantyl mesityl phenyl 2-adamantyl 2-adamantyl 2-tert-butylphenyl phenyl 2-adamantyl 2-adamantyl 3-tert-butylphenyl phenyl 2-adamantyl 2-adamantyl 4-tert-butylphenyl phenyl 2-adamantyl 2-adamantyl 2-ethenylphenyl phenyl 2-adamantyl 2-adamantyl 3-ethenylphenyl phenyl 2-adamantyl 2-adamantyl 4-ethenylphenyl phenyl 2-adamantyl 2-adamantyl 2-biphenylyl phenyl 2-adamantyl 2-adamantyl 3-biphenylyl phenyl 2-adamantyl 2-adamantyl 4-biphenylyl phenyl 2-adamantyl 2-adamantyl 1-naphthyl phenyl 2-adamantyl 2-adamantyl 2-naphthyl phenyl 2-adamantyl 2-adamantyl 1,1′-binaphthalene-2-yl phenyl 2-adamantyl 2-adamantyl 2-methoxyphenyl phenyl 2-adamantyl 2-adamantyl 3-methoxyphenyl phenyl 2-adamantyl 2-adamantyl 4-methoxyphenyl phenyl 2-adamantyl 2-adamantyl 2-tert-butoxyphenyl phenyl 2-adamantyl 2-adamantyl 3-tert-butoxyphenyl phenyl 2-adamantyl 2-adamantyl 4-tert-butoxyphenyl phenyl 2-adamantyl 2-adamantyl 2- phenyl dimethylaminophenyl 2-adamantyl 2-adamantyl 3- phenyl dimethylaminophenyl

TABLE 26 Table 14-3 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 2-adamantyl 2-adamantyl 4-dimethyl- phenyl aminophenyl 2-adamantyl 2-adamantyl 2′-dimethylamino-2- phenyl biphenylyl 2-adamantyl 2-adamantyl 8-dimethylamino-1- phenyl naphthyl 2-adamantyl 2-adamantyl 2′-dimethylamino-1,1′- phenyl binaphthalene-2-yl 2-adamantyl 2-adamantyl benzyl phenyl 2-adamantyl 2-adamantyl 1-phenylethyl phenyl 2-adamantyl 2-adamantyl 2-phenylethyl phenyl 2-adamantyl 2-adamantyl 2-ethenylbenzyl phenyl 2-adamantyl 2-adamantyl 3-ethenylbenzyl phenyl 2-adamantyl 2-adamantyl 4-ethenylbenzyl phenyl 2-adamantyl 2-adamantyl 4-(2-ethenyl- phenyl phenyl)butyl 2-adamantyl 2-adamantyl 4-(3-ethenyl- phenyl phenyl)butyl 2-adamantyl 2-adamantyl 4-(4-ethenyl- phenyl phenyl)butyl 2-adamantyl 2-adamantyl vinyl phenyl 2-adamantyl 2-adamantyl methallyl phenyl 2-adamantyl 2-adamantyl 1-octenyl phenyl 2-adamantyl 2-adamantyl ethynyl phenyl 2-adamantyl 2-adamantyl 1-propynyl phenyl 2-adamantyl 2-adamantyl 1-octynyl phenyl 2-adamantyl 2-adamantyl allyl phenyl 2-adamantyl 2-adamantyl 2-octenyl phenyl

TABLE 27 Table 15-1 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-butyl tert-butyl hydrogen para-tolyl tert-butyl tert-butyl methyl para-tolyl 157–166 tert-butyl tert-butyl ethyl para-tolyl tert-butyl tert-butyl n-propyl para-tolyl tert-butyl tert-butyl n-butyl para-tolyl tert-butyl tert-butyl isobutyl para-tolyl tert-butyl tert-butyl n-pentyl para-tolyl tert-butyl tert-butyl isopentyl para-tolyl tert-butyl tert-butyl n-hexyl para-tolyl tert-butyl tert-butyl 2-methyl-1-pentyl para-tolyl tert-butyl tert-butyl 2,2-diethyl-1-ethyl para-tolyl tert-butyl tert-butyl n-heptyl para-tolyl tert-butyl tert-butyl n-octyl para-tolyl tert-butyl tert-butyl isopropyl para-tolyl tert-butyl tert-butyl sec-butyl para-tolyl tert-butyl tert-butyl 2-pentyl para-tolyl tert-butyl tert-butyl 3-pentyl para-tolyl tert-butyl tert-butyl 2-hexyl para-tolyl tert-butyl tert-butyl 3-hexyl para-tolyl tert-butyl tert-butyl tert-butyl para-tolyl 179–201 tert-butyl tert-butyl tert-amyl para-tolyl tert-butyl tert-butyl 1,1-dimethylbutyl para-tolyl tert-butyl tert-butyl 3-methyl-3-pentyl para-tolyl tert-butyl tert-butyl 1,1,2-trimethylpropyl para-tolyl tert-butyl tert-butyl 1-adamantyl para-tolyl tert-butyl tert-butyl 2-methyl-1-adamantyl para-tolyl tert-butyl tert-butyl cyclopropyl para-tolyl tert-butyl tert-butyl cyclopentyl para-tolyl tert-butyl tert-butyl cyclohexyl para-tolyl tert-butyl tert-butyl 1-methylcyclohexyl para-tolyl tert-butyl tert-butyl 2-methylcyclohexyl para-tolyl tert-butyl tert-butyl 2-adamantyl para-tolyl tert-butyl tert-butyl 1-methyl-2-adamantyl para-tolyl tert-butyl tert-butyl 2-methyl-2-adamantyl para-tolyl tert-butyl tert-butyl phenyl para-tolyl

TABLE 28 Table 15-2 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-butyl tert-butyl ortho-tolyl para-tolyl tert-butyl tert-butyl meta-tolyl para-tolyl tert-butyl tert-butyl para-tolyl para-tolyl tert-butyl tert-butyl 2,3-xylyl para-tolyl tert-butyl tert-butyl 2,4-xylyl para-tolyl tert-butyl tert-butyl 2,5-xylyl para-tolyl tert-butyl tert-butyl 2,6-xylyl para-tolyl tert-butyl tert-butyl 3,4-xylyl para-tolyl tert-butyl tert-butyl 3,5-xylyl para-tolyl tert-butyl tert-butyl mesityl para-tolyl tert-butyl tert-butyl 2-tert-butylphenyl para-tolyl tert-butyl tert-butyl 3-tert-butylphenyl para-tolyl tert-butyl tert-butyl 4-tert-butylphenyl para-tolyl tert-butyl tert-butyl 2-ethenylphenyl para-tolyl tert-butyl tert-butyl 3-ethenylphenyl para-tolyl tert-butyl tert-butyl 4-ethenylphenyl para-tolyl tert-butyl tert-butyl 2-biphenylyl para-tolyl tert-butyl tert-butyl 3-biphenylyl para-tolyl tert-butyl tert-butyl 4-biphenylyl para-tolyl tert-butyl tert-butyl 1-naphthyl para-tolyl tert-butyl tert-butyl 2-naphthyl para-tolyl tert-butyl tert-butyl 1,1′-binaphthalene-2-yl para-tolyl tert-butyl tert-butyl 2-methoxyphenyl para-tolyl tert-butyl tert-butyl 3-methoxyphenyl para-tolyl tert-butyl tert-butyl 4-methoxyphenyl para-tolyl tert-butyl tert-butyl 2-tert-butoxyphenyl para-tolyl tert-butyl tert-butyl 3-tert-butoxyphenyl para-tolyl tert-butyl tert-butyl 4-tert-butoxyphenyl para-tolyl tert-butyl tert-butyl 2-dimethylaminophenyl para-tolyl tert-butyl tert-butyl 3-dimethylaminophenyl para-tolyl

TABLE 29 Table 15-3 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-butyl tert-butyl 4-dimethyl- para-tolyl aminophenyl tert-butyl tert-butyl 2′-dimethylamino-2- para-tolyl biphenylyl tert-butyl tert-butyl 8-dimethylamino-1- para-tolyl naphthyl tert-butyl tert-butyl 2′-dimethylamino- para-tolyl 1,1′-binaphthalene- 2-yl tert-butyl tert-butyl benzyl para-tolyl tert-butyl tert-butyl 1-phenylethyl para-tolyl tert-butyl tert-butyl 2-phenylethyl para-tolyl tert-butyl tert-butyl 2-ethenylbenzyl para-tolyl tert-butyl tert-butyl 3-ethenylbenzyl para-tolyl tert-butyl tert-butyl 4-ethenylbenzyl para-tolyl tert-butyl tert-butyl 4-(2-ethenyl- para-tolyl phenyl)butyl tert-butyl tert-butyl 4-(3-ethenyl- para-tolyl phenyl)butyl tert-butyl tert-butyl 4-(4-ethenyl- para-tolyl phenyl)butyl tert-butyl tert-butyl vinyl para-tolyl tert-butyl tert-butyl methallyl para-tolyl tert-butyl tert-butyl 1-octenyl para-tolyl tert-butyl tert-butyl ethynyl para-tolyl tert-butyl tert-butyl 1-propynyl para-tolyl tert-butyl tert-butyl 1-octynyl para-tolyl tert-butyl tert-butyl allyl para-tolyl tert-butyl tert-butyl 2-octenyl para-tolyl isopropyl isopropyl isopropyl para-tolyl n-butyl cyclohexyl cyclohexyl para-tolyl cyclopentyl cyclopentyl cyclopentyl para-tolyl cyclohexyl cyclohexyl cyclohexyl para-tolyl 129–131

TABLE 30 Table 16-1 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-amyl tert-amyl hydrogen para-tolyl tert-amyl tert-amyl methyl para-tolyl tert-amyl tert-amyl ethyl para-tolyl tert-amyl tert-amyl n-propyl para-tolyl tert-amyl tert-amyl n-butyl para-tolyl tert-amyl tert-amyl isobutyl para-tolyl tert-amyl tert-amyl n-pentyl para-tolyl tert-amyl tert-amyl isopentyl para-tolyl tert-amyl tert-amyl n-hexyl para-tolyl tert-amyl tert-amyl 2-methyl-1-pentyl para-tolyl tert-amyl tert-amyl 2,2-diethyl-1-ethyl para-tolyl tert-amyl tert-amyl n-heptyl para-tolyl tert-amyl tert-amyl n-octyl para-tolyl tert-amyl tert-amyl isopropyl para-tolyl tert-amyl tert-amyl sec-butyl para-tolyl tert-amyl tert-amyl 2-pentyl para-tolyl tert-amyl tert-amyl 3-pentyl para-tolyl tert-amyl tert-amyl 2-hexyl para-tolyl tert-amyl tert-amyl 3-hexyl para-tolyl tert-amyl tert-amyl tert-butyl para-tolyl tert-amyl tert-amyl tert-amyl para-tolyl tert-amyl tert-amyl 1,1-dimethylbutyl para-tolyl tert-amyl tert-amyl 3-methyl-3-pentyl para-tolyl tert-amyl tert-amyl 1,1,2-trimethylpropyl para-tolyl tert-amyl tert-amyl 1-adamantyl para-tolyl tert-amyl tert-amyl 2-methyl-1-adamantyl para-tolyl tert-amyl tert-amyl cyclopropyl para-tolyl tert-amyl tert-amyl cyclopentyl para-tolyl tert-amyl tert-amyl cyclohexyl para-tolyl tert-amyl tert-amyl 1-methylcyclohexyl para-tolyl tert-amyl tert-amyl 2-methylcyclohexyl para-tolyl tert-amyl tert-amyl 2-adamantyl para-tolyl tert-amyl tert-amyl 1-methyl-2-adamantyl para-tolyl tert-amyl tert-amyl 2-methyl-2-adamantyl para-tolyl tert-amyl tert-amyl phenyl para-tolyl

TABLE 31 Table 16-2 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-amyl tert-amyl ortho-tolyl para-tolyl tert-amyl tert-amyl meta-tolyl para-tolyl tert-amyl tert-amyl para-tolyl para-tolyl tert-amyl tert-amyl 2,3-xylyl para-tolyl tert-amyl tert-amyl 2,4-xylyl para-tolyl tert-amyl tert-amyl 2,5-xylyl para-tolyl tert-amyl tert-amyl 2,6-xylyl para-tolyl tert-amyl tert-amyl 3,4-xylyl para-tolyl tert-amyl tert-amyl 3,5-xylyl para-tolyl tert-amyl tert-amyl mesityl para-tolyl tert-amyl tert-amyl 2-tert-butylphenyl para-tolyl tert-amyl tert-amyl 3-tert-butylphenyl para-tolyl tert-amyl tert-amyl 4-tert-butylphenyl para-tolyl tert-amyl tert-amyl 2-ethenylphenyl para-tolyl tert-amyl tert-amyl 3-ethenylphenyl para-tolyl tert-amyl tert-amyl 4-ethenylphenyl para-tolyl tert-amyl tert-amyl 2-biphenylyl para-tolyl tert-amyl tert-amyl 3-biphenylyl para-tolyl tert-amyl tert-amyl 4-biphenylyl para-tolyl tert-amyl tert-amyl 1-naphthyl para-tolyl tert-amyl tert-amyl 2-naphthyl para-tolyl tert-amyl tert-amyl 1,1′-binaphthalene-2-yl para-tolyl tert-amyl tert-amyl 2-methoxyphenyl para-tolyl tert-amyl tert-amyl 3-methoxyphenyl para-tolyl tert-amyl tert-amyl 4-methoxyphenyl para-tolyl tert-amyl tert-amyl 2-tert-butoxyphenyl para-tolyl tert-amyl tert-amyl 3-tert-butoxyphenyl para-tolyl tert-amyl tert-amyl 4-tert-butoxyphenyl para-tolyl tert-amyl tert-amyl 2-dimethylaminophenyl para-tolyl tert-amyl tert-amyl 3-dimethylaminophenyl para-tolyl

TABLE 32 Table 16-3 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) tert-amyl tert-amyl 4-dimethylaminophenyl para-tolyl tert-amyl tert-amyl 2′-dimethylamino-2- para-tolyl biphenylyl tert-amyl tert-amyl 8-dimethylamino-1- para-tolyl naphthyl tert-amyl tert-amyl 2′-dimethylamino-1,1′- para-tolyl binaphthalene-2-yl tert-amyl tert-amyl benzyl para-tolyl tert-amyl tert-amyl 1-phenylethyl para-tolyl tert-amyl tert-amyl 2-phenylethyl para-tolyl tert-amyl tert-amyl 2-ethenylbenzyl para-tolyl tert-amyl tert-amyl 3-ethenylbenzyl para-tolyl tert-amyl tert-amyl 4-ethenylbenzyl para-tolyl tert-amyl tert-amyl 4-(2-ethenylphenyl)butyl para-tolyl tert-amyl tert-amyl 4-(3-ethenylphenyl)butyl para-tolyl tert-amyl tert-amyl 4-(4-ethenylphenyl)butyl para-tolyl tert-amyl tert-amyl vinyl para-tolyl tert-amyl tert-amyl methallyl para-tolyl tert-amyl tert-amyl 1-octenyl para-tolyl tert-amyl tert-amyl ethynyl para-tolyl tert-amyl tert-amyl 1-propynyl para-tolyl tert-amyl tert-amyl 1-octynyl para-tolyl tert-amyl tert-amyl allyl para-tolyl tert-amyl tert-amyl 2-octenyl para-tolyl

TABLE 33 Table 17-1 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 1-adamantyl 1-adamantyl hydrogen para-tolyl 1-adamantyl 1-adamantyl methyl para-tolyl 1-adamantyl 1-adamantyl ethyl para-tolyl 1-adamantyl 1-adamantyl n-propyl para-tolyl 1-adamantyl 1-adamantyl n-butyl para-tolyl 1-adamantyl 1-adamantyl isobutyl para-tolyl 1-adamantyl 1-adamantyl n-pentyl para-tolyl 1-adamantyl 1-adamantyl isopentyl para-tolyl 1-adamantyl 1-adamantyl n-hexyl para-tolyl 1-adamantyl 1-adamantyl 2-methyl-1-pentyl para-tolyl 1-adamantyl 1-adamantyl 2,2-diethyl-1-ethyl para-tolyl 1-adamantyl 1-adamantyl n-heptyl para-tolyl 1-adamantyl 1-adamantyl n-octyl para-tolyl 1-adamantyl 1-adamantyl isopropyl para-tolyl 1-adamantyl 1-adamantyl sec-butyl para-tolyl 1-adamantyl 1-adamantyl 2-pentyl para-tolyl 1-adamantyl 1-adamantyl 3-pentyl para-tolyl 1-adamantyl 1-adamantyl 2-hexyl para-tolyl 1-adamantyl 1-adamantyl 3-hexyl para-tolyl 1-adamantyl 1-adamantyl tert-butyl para-tolyl 1-adamantyl 1-adamantyl tert-amyl para-tolyl 1-adamantyl 1-adamantyl 1,1-dimethylbutyl para-tolyl 1-adamantyl 1-adamantyl 3-methyl-3-pentyl para-tolyl 1-adamantyl 1-adamantyl 1,1,2- para-tolyl trimethylpropyl 1-adamantyl 1-adamantyl 1-adamantyl para-tolyl 1-adamantyl 1-adamantyl 2-methyl-1- para-tolyl adamantyl 1-adamantyl 1-adamantyl cyclopropyl para-tolyl 1-adamantyl 1-adamantyl cyclopentyl para-tolyl 1-adamantyl 1-adamantyl cyclohexyl para-tolyl 1-adamantyl 1-adamantyl 1-methylcyclohexyl para-tolyl 1-adamantyl 1-adamantyl 2-methylcyclohexyl para-tolyl 1-adamantyl 1-adamantyl 2-adamantyl para-tolyl 1-adamantyl 1-adamantyl 1-methyl-2- para-tolyl adamantyl 1-adamantyl 1-adamantyl 2-methyl-2- para-tolyl adamantyl 1-adamantyl 1-adamantyl phenyl para-tolyl

TABLE 34 Table 17-2 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 1-adamantyl 1-adamantyl ortho-tolyl para-tolyl 1-adamantyl 1-adamantyl meta-tolyl para-tolyl 1-adamantyl 1-adamantyl para-tolyl para-tolyl 1-adamantyl 1-adamantyl 2,3-xylyl para-tolyl 1-adamantyl 1-adamantyl 2,4-xylyl para-tolyl 1-adamantyl 1-adamantyl 2,5-xylyl para-tolyl 1-adamantyl 1-adamantyl 2,6-xylyl para-tolyl 1-adamantyl 1-adamantyl 3,4-xylyl para-tolyl 1-adamantyl 1-adamantyl 3,5-xylyl para-tolyl 1-adamantyl 1-adamantyl mesityl para-tolyl 1-adamantyl 1-adamantyl 2-tert-butylphenyl para-tolyl 1-adamantyl 1-adamantyl 3-tert-butylphenyl para-tolyl 1-adamantyl 1-adamantyl 4-tert-butylphenyl para-tolyl 1-adamantyl 1-adamantyl 2-ethenylphenyl para-tolyl 1-adamantyl 1-adamantyl 3-ethenylphenyl para-tolyl 1-adamantyl 1-adamantyl 4-ethenylphenyl para-tolyl 1-adamantyl 1-adamantyl 2-biphenylyl para-tolyl 1-adamantyl 1-adamantyl 3-biphenylyl para-tolyl 1-adamantyl 1-adamantyl 4-biphenylyl para-tolyl 1-adamantyl 1-adamantyl 1-naphthyl para-tolyl 1-adamantyl 1-adamantyl 2-naphthyl para-tolyl 1-adamantyl 1-adamantyl 1,1′-binaphthalene- para-tolyl 2-yl 1-adamantyl 1-adamantyl 2-methoxyphenyl para-tolyl 1-adamantyl 1-adamantyl 3-methoxyphenyl para-tolyl 1-adamantyl 1-adamantyl 4-methoxyphenyl para-tolyl 1-adamantyl 1-adamantyl 2-tert-butoxyphenyl para-tolyl 1-adamantyl 1-adamantyl 3-tert-butoxyphenyl para-tolyl 1-adamantyl 1-adamantyl 4-tert-butoxyphenyl para-tolyl 1-adamantyl 1-adamantyl 2-dimethyl- para-tolyl aminophenyl 1-adamantyl 1-adamantyl 3-dimethyl- para-tolyl aminophenyl

TABLE 35 Table 17-3 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 1-adamantyl 1-adamantyl 4-dimethyl- para-tolyl aminophenyl 1-adamantyl 1-adamantyl 2′-dimethylamino-2- para-tolyl biphenylyl 1-adamantyl 1-adamantyl 8-dimethylamino-1- para-tolyl naphthyl 1-adamantyl 1-adamantyl 2′-dimethylamino- para-tolyl 1,1′-binaphthalene- 2-yl 1-adamantyl 1-adamantyl benzyl para-tolyl 1-adamantyl 1-adamantyl 1-phenylethyl para-tolyl 1-adamantyl 1-adamantyl 2-phenylethyl para-tolyl 1-adamantyl 1-adamantyl 2-ethenylbenzyl para-tolyl 1-adamantyl 1-adamantyl 3-ethenylbenzyl para-tolyl 1-adamantyl 1-adamantyl 4-ethenylbenzyl para-tolyl 1-adamantyl 1-adamantyl 4-(2- para-tolyl ethenylphenyl)butyl 1-adamantyl 1-adamantyl 4-(3- para-tolyl ethenylphenyl)butyl 1-adamantyl 1-adamantyl 4-(4- para-tolyl ethenylphenyl)butyl 1-adamantyl 1-adamantyl vinyl para-tolyl 1-adamantyl 1-adamantyl methallyl para-tolyl 1-adamantyl 1-adamantyl 1-octenyl para-tolyl 1-adamantyl 1-adamantyl ethynyl para-tolyl 1-adamantyl 1-adamantyl 1-propynyl para-tolyl 1-adamantyl 1-adamantyl 1-octynyl para-tolyl 1-adamantyl 1-adamantyl allyl para-tolyl 1-adamantyl 1-adamantyl 2-octenyl para-tolyl

TABLE 36 Table 18-1 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 2-adamantyl 2-adamantyl hydrogen para-tolyl 2-adamantyl 2-adamantyl methyl para-tolyl 2-adamantyl 2-adamantyl ethyl para-tolyl 2-adamantyl 2-adamantyl n-propyl para-tolyl 2-adamantyl 2-adamantyl n-butyl para-tolyl 2-adamantyl 2-adamantyl isobutyl para-tolyl 2-adamantyl 2-adamantyl n-pentyl para-tolyl 2-adamantyl 2-adamantyl isopentyl para-tolyl 2-adamantyl 2-adamantyl n-hexyl para-tolyl 2-adamantyl 2-adamantyl 2-methyl-1-pentyl para-tolyl 2-adamantyl 2-adamantyl 2,2-diethyl-1-ethyl para-tolyl 2-adamantyl 2-adamantyl n-heptyl para-tolyl 2-adamantyl 2-adamantyl n-octyl para-tolyl 2-adamantyl 2-adamantyl isopropyl para-tolyl 2-adamantyl 2-adamantyl sec-butyl para-tolyl 2-adamantyl 2-adamantyl 2-pentyl para-tolyl 2-adamantyl 2-adamantyl 3-pentyl para-tolyl 2-adamantyl 2-adamantyl 2-hexyl para-tolyl 2-adamantyl 2-adamantyl 3-hexyl para-tolyl 2-adamantyl 2-adamantyl tert-butyl para-tolyl 2-adamantyl 2-adamantyl tert-amyl para-tolyl 2-adamantyl 2-adamantyl 1,1-dimethylbutyl para-tolyl 2-adamantyl 2-adamantyl 3-methyl-3-pentyl para-tolyl 2-adamantyl 2-adamantyl 1,1,2- para-tolyl trimethylpropyl 2-adamantyl 2-adamantyl 1-adamantyl para-tolyl 2-adamantyl 2-adamantyl 2-methyl-1- para-tolyl adamantyl 2-adamantyl 2-adamantyl cyclopropyl para-tolyl 2-adamantyl 2-adamantyl cyclopentyl para-tolyl 2-adamantyl 2-adamantyl cyclohexyl para-tolyl 2-adamantyl 2-adamantyl 1-methylcyclohexyl para-tolyl 2-adamantyl 2-adamantyl 2-methylcyclohexyl para-tolyl 2-adamantyl 2-adamantyl 2-adamantyl para-tolyl 2-adamantyl 2-adamantyl 1-methyl-2- para-tolyl adamantyl 2-adamantyl 2-adamantyl 2-methyl-2- para-tolyl adamantyl 2-adamantyl 2-adamantyl phenyl para-tolyl

TABLE 37 Table 18-2 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 2-adamantyl 2-adamantyl ortho-tolyl para-tolyl 2-adamantyl 2-adamantyl meta-tolyl para-tolyl 2-adamantyl 2-adamantyl para-tolyl para-tolyl 2-adamantyl 2-adamantyl 2,3-xylyl para-tolyl 2-adamantyl 2-adamantyl 2,4-xylyl para-tolyl 2-adamantyl 2-adamantyl 2,5-xylyl para-tolyl 2-adamantyl 2-adamantyl 2,6-xylyl para-tolyl 2-adamantyl 2-adamantyl 3,4-xylyl para-tolyl 2-adamantyl 2-adamantyl 3,5-xylyl para-tolyl 2-adamantyl 2-adamantyl mesityl para-tolyl 2-adamantyl 2-adamantyl 2-tert-butylphenyl para-tolyl 2-adamantyl 2-adamantyl 3-tert-butylphenyl para-tolyl 2-adamantyl 2-adamantyl 4-tert-butylphenyl para-tolyl 2-adamantyl 2-adamantyl 2-ethenylphenyl para-tolyl 2-adamantyl 2-adamantyl 3-ethenylphenyl para-tolyl 2-adamantyl 2-adamantyl 4-ethenylphenyl para-tolyl 2-adamantyl 2-adamantyl 2-biphenylyl para-tolyl 2-adamantyl 2-adamantyl 3-biphenylyl para-tolyl 2-adamantyl 2-adamantyl 4-biphenylyl para-tolyl 2-adamantyl 2-adamantyl 1-naphthyl para-tolyl 2-adamantyl 2-adamantyl 2-naphthyl para-tolyl 2-adamantyl 2-adamantyl 1,1′-binaphthalene- para-tolyl 2-yl 2-adamantyl 2-adamantyl 2-methoxyphenyl para-tolyl 2-adamantyl 2-adamantyl 3-methoxyphenyl para-tolyl 2-adamantyl 2-adamantyl 4-methoxyphenyl para-tolyl 2-adamantyl 2-adamantyl 2-tert-butoxyphenyl para-tolyl 2-adamantyl 2-adamantyl 3-tert-butoxyphenyl para-tolyl 2-adamantyl 2-adamantyl 4-tert-butoxyphenyl para-tolyl 2-adamantyl 2-adamantyl 2-dimethyl- para-tolyl aminophenyl 2-adamantyl 2-adamantyl 3-dimethyl- para-tolyl aminophenyl

TABLE 38 Table 18-3 Melting point (° C.) (Decomp. R¹ R² R³ Ar temp.) 2-adamantyl 2-adamantyl 4-dimethyl- para-tolyl aminophenyl 2-adamantyl 2-adamantyl 2′-dimethylamino-2- para-tolyl biphenylyl 2-adamantyl 2-adamantyl 8-dimethylamino- para-tolyl 1-naphthyl 2-adamantyl 2-adamantyl 2′-dimethylamino-1, para-tolyl 1′-binaphthalene-2- yl 2-adamantyl 2-adamantyl benzyl para-tolyl 2-adamantyl 2-adamantyl 1-phenylethyl para-tolyl 2-adamantyl 2-adamantyl 2-phenylethyl para-tolyl 2-adamantyl 2-adamantyl 2-ethenylbenzyl para-tolyl 2-adamantyl 2-adamantyl 3-ethenylbenzyl para-tolyl 2-adamantyl 2-adamantyl 4-ethenylbenzyl para-tolyl 2-adamantyl 2-adamantyl 4-(2-ethenylphenyl) para-tolyl butyl 2-adamantyl 2-adamantyl 4-(3-ethenylphenyl) para-tolyl butyl 2-adamantyl 2-adamantyl 4-(4-ethenylphenyl) para-tolyl butyl 2-adamantyl 2-adamantyl vinyl para-tolyl 2-adamantyl 2-adamantyl methallyl para-tolyl 2-adamantyl 2-adamantyl 1-octenyl para-tolyl 2-adamantyl 2-adamantyl ethynyl para-tolyl 2-adamantyl 2-adamantyl 1-propynyl para-tolyl 2-adamantyl 2-adamantyl 1-octynyl para-tolyl 2-adamantyl 2-adamantyl allyl para-tolyl 2-adamantyl 2-adamantyl 2-octenyl para-tolyl

EXAMPLES

The present invention will be described with reference to the following examples, but it should be construed that the invention is in no way limited to the examples. The processes for producing a phosphonium borate compound, the novel phosphonium borate compounds, and the use of the compounds will be described by Examples A relating to trialkylphosphonium tetraphenylborates and Examples B relating to novel phosphonium borate compounds.

Example A-1 Production of tri-tert-butylphosphonium tetraphenylborate

A 30-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. 8.1 g (40 mmol) of tri-tert-butylphosphine and 8.1 ml of heptane were weighed in the flask, followed by stirring to dissolve tri-tert-butylphosphine. While the stirring was continuously carried out, 8.0 ml (40 mmol) of 5N hydrochloric acid was added to the solution, and the mixture was stirred at 25° C. for 1 hour. Thereafter, the organic phase was analyzed by gas chromatography, which confirmed the disappearance of tri-tert-butylphosphine, and the reaction was completed. After the completion of the reaction, the liquid was separated. The aqueous phase was washed with 8.1 ml of heptane. The aqueous phase was assumed to contain tri-tert-butylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 15.1 g (44 mmol) of sodium tetraphenylborate and 60 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of tri-tert-butylphosphine hydrochloride was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 18.2 g of objective tri-tert-butylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 87% based on tri-tert-butylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be tri-tert-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 185-201° C. (decomposition)

(2) ¹H-NMR spectrum (δ in DMSO-d6) 1.54 ppm (d, 27H, J=15.2 Hz, H₃C—C—P) 5.23-7.07 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.34 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.18 ppm (brs, 8H, Ph-B)

(3) ¹³C-NMR spectrum (δ in DMSO-d6) 29.3 ppm (s, H₃C—C—P) 36.3 ppm (d, J=28.6 Hz, H₃C—C—P) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=3.1 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

(4) IR spectrum (KBr) 2395 cm⁻¹

Example A-2 Production of tri-tert-butylphosphonium tetraphenylborate

A 30-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. 8.1 g (40 mmol) of tri-tert-butylphosphine and 8.1 ml of heptane were weighed in the flask, followed by stirring to dissolve tri-tert-butylphosphine. While the stirring was continuously carried out, 11.0 ml (22 mmol) of 4N sulfuric acid was added to the solution, and the mixture was stirred at 25° C. for 1 hour. Thereafter, the organic phase was analyzed by gas chromatography, which confirmed the disappearance of tri-tert-butylphosphine, and the reaction was completed. After the completion of the reaction, the liquid was separated. The aqueous phase was washed with 8.1 ml of heptane. The aqueous phase was assumed to contain tri-tert-butylphosphine sulfate dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 16.4 g (48 mmol) of sodium tetraphenylborate and 66 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of tri-tert-butylphosphine sulfate was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 19.4 g of objective tri-tert-butylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 93% based on tri-tert-butylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be tri-tert-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 185-201° C. (decomposition)

(2) ¹H-NMR spectrum (δ in DMSO-d6) 1.54 ppm (d, 27H, J=15.2 Hz, H₃C—C—P) 5.23-7.07 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.34 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.18 ppm (brs, 8H, Ph-B)

(3) ¹³C-NMR spectrum (δ in DMSO-d6) 29.3 ppm (s, H₃C—C—P) 36.3 ppm (d, J=28.6 Hz, H₃C—C—P) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=3.1 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

(4) IR spectrum (KBr) 2395 cm⁻¹

Example A-3 Production of tri-n-butylphosphonium tetraphenylborate

The procedures in Example A-1 were repeated except that 8.1 g (40 mmol) of tri-tert-butylphosphine was replaced with 8.1 g (40 mmol) of tri-n-butylphosphine. Consequently, 18.8 g of objective tri-n-butylphosphonium tetraphenylborate was obtained as white crystal. The yield (mol %) was 90% based on tri-n-butylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be tri-n-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 114-116° C. (decomposition)

(2) ¹H-NMR spectrum (δ in DMSO-d6) 0.91 ppm (t, 9H, J=7.15 Hz, H₃C—(CH₂)₃—P) 1.33-1.46 ppm (m, 6H, H₃C—(CH₂)₃—P) 1.48-1.60 ppm (m, 6H, H₃C—(CH₂)₃—P) 2.10-2.30 ppm (m, 6H, H₃C—(CH₂)₃—P) 5.34-7.18 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.06 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.06 Hz, Ph-B) 7.18 ppm (brs, 8H, Ph-B)

(3) ¹³C-NMR spectrum (δ in DMSO-d6) 13.1 ppm (s, H₃C—CH₂—CH₂—CH₂—P) 15.8 ppm (d, J=46.0 Hz, H₃C—CH₂—CH₂—CH₂—P) 23.0 ppm (d, J=15.5 Hz, H₃C—CH₂—CH₂—CH₂—P) 23.9 ppm (d, J=4.4 Hz, H₃C—CH₂—CH₂—CH₂—P) 121.5 ppm (s, Ph-B) 125.3 ppm (dd, J=2.5 Hz, 5.0 Hz, Ph-B) 135.7 ppm (s, Ph-B) 163.5 ppm (dd, J=49.1 Hz, 98.8 Hz, Ph quaternary-B)

(4) IR spectrum (KBr) 2361 cm⁻¹

Example A-4 Production of tricyclohexylphosphonium tetraphenylborate

The procedures in Example A-1 were repeated except that 8.1 g (40 mmol) of tri-tert-butylphosphine was replaced with 11.2 g (40 mmol) of tricyclohexylphosphine. Consequently, 21.4 g of objective tricyclohexylphosphonium tetraphenylborate was obtained as white crystal. The yield (mol %) was 89% based on tricyclohexylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be tricyclohexylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 171-177° C. (decomposition)

(2) ¹H-NMR spectrum (δ in DMSO-d6) 1.17-1.89 ppm (m, 30H, cyclohexyl secondary) 2.43-2.56 ppm (m, 3H, cyclohexyl tertiary) 5.76 ppm (brd, 1H, J=470.6 Hz, H—P) 6.79 ppm (t, 4H, J=7.34 Hz, Ph-B) 6.93 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.19 ppm (brs, 8H, Ph-B)

(3) ¹³C-NMR spectrum (δ in DMSO-d6) 24.6 ppm (d, J=1.2 Hz, cyclohexyl secondary) 25.6 ppm (d, J=13.1 Hz, cyclohexyl secondary) 26.9 ppm (d, J=39.8 Hz, cyclohexyl tertiary) 27.0 ppm (d, J=3.1 Hz, cyclohexyl secondary) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=3.1 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.1 Hz, 98.8 Hz, Ph quaternary-B)

(4) IR spectrum (KBr) 2359 cm⁻¹

Example A-5 Synthesis of 2-ortho-tolylpyridine from 2-chloropyridine and ortho-tolylboronic acid Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.568 g (5 mmol) of 2-chloropyridine, 0.748 g (5.5 mmol) of ortho-tolylboronic acid, 0.011 g (0.05 mmol) of palladium (II) acetate, 0.959 g (17 mmol) of potassium fluoride and 10 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 24 hours. After the completion of the reaction, 10 ml of 10% aqueous sodium hydroxide solution was added, followed by separation. The organic phase was purified by column chromatography to afford 0.711 g of 2-ortho-tolylpyridine (yield: 84 mol % based on 2-chloropyridine). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 169 (M⁺)

Example A-6 Synthesis of 4-methylbiphenyl from 4-bromotoluene and phenylmagnesium chloride Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 0.014 g (0.08 mmol) of palladium (II) chloride, 0.0194 g (0.19 mmol) of triethylamine and 5.5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.084 g (0.16 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 21° C. for 30 minutes. 1.368 g (8 mmol) of 4-bromotoluene was added, followed by stirring at 21° C. for 30 minutes. 4 ml (8.8 mmol) of 2.2M tetrahydrofuran solution of phenylmagnesium chloride was added dropwise at 21° C. over a period of 10 minutes, followed by stirring at 21° C. for 2 hours. After the completion of the reaction, 5 ml of saturated aqueous ammonium chloride solution was added, followed by separation. The organic phase was purified by column chromatography to afford 1.175 g of 4-methylbiphenyl (yield: 87 mol % based on 4-bromotoluene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 168 (M⁺)

Example A-7 Synthesis of 4-vinylbiphenyl from bromobenzene and 4-vinylphenylmagnesium chloride Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 0.0674 g (0.3 mmol) of palladium (II) acetate and 6 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.314 g (0.6 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 19° C. for 30 minutes. 4.710 g (30 mmol) of bromobenzene was added, followed by stirring at 19° C. for 30 minutes. 40 ml (50 mmol) of 1.25M tetrahydrofuran solution of 4-vinylphenylmagnesium chloride was added dropwise at 19° C. over a period of 2 hours, followed by stirring at 30° C. for 2 hours. After the completion of the reaction, 10 ml of saturated aqueous ammonium chloride solution was added, followed by separation. The organic phase was purified by column chromatography to afford 4.450 g of 4-vinylbiphenyl (yield: 82 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 180 (M⁺)

Example A-8 Synthesis of 1-phenylheptane from n-heptyl chloride and phenylmagnesium chloride Synthesis in which tricyclohexylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 0.027 g (0.12 mmol) of palladium (II) acetate and 7 ml of N-methylpyrrolidinone were weighed in the flask, followed by stirring. Further, 0.072 g (0.12 mmol) of tricyclohexylphosphonium tetraphenylborate obtained in Example A-4 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.404 g (3 mmol) of n-heptyl chloride was added, followed by stirring at 25° C. for 30 minutes. 2 ml (4.4 mmol) of 2.2M tetrahydrofuran solution of phenylmagnesium chloride was added dropwise at 25° C. over a period of 10 minutes, followed by stirring at 25° C. for 19 hours. After the completion of the reaction, 6 ml of tetrahydrofuran and 10 ml of saturated aqueous ammonium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.435 g of 1-phenylheptane (yield: 82 mol % based on n-heptyl chloride). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Example A-9 Synthesis of 4-cyanobiphenyl from 4-chlorobenzonitrile and phenylzinc chloride Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate and 7 ml of N-methylpyrrolidinone were weighed in the flask, followed by stirring. Further, 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes to prepare a reaction liquid.

A 50-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 1.090 g (8 mmol) of zinc chloride and 4 ml of N-methylpyrrolidinone were weighed in the flask. The flask was purged with argon, followed by stirring. 3.4 ml (7.5 mmol) of 2.2M tetrahydrofuran solution of phenylmagnesium chloride was added dropwise at 25° C. over a period of 30 minutes, followed by stirring at 25° C. for 30 minutes. The reaction liquid previously obtained was added, followed by stirring at 25° C. for 30 minutes. Further, 0.688 g (5 mmol) of 4-chlorobenzonitrile was added, followed by stirring at 120° C. for 9 hours. After the completion of the reaction, 10 ml of toluene and 10 ml of saturated aqueous ammonium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.670 g of 4-cyanobiphenyl (yield: 75 mol % based on 4-chlorobenzonitrile). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 179 (M⁺)

Example A-10 Synthesis of 1-phenylheptane from chlorobenzene and n-heptylzinc chloride Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate and 7 ml of N-methylpyrrolidinone were weighed in the flask, followed by stirring. Further, 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes to prepare a reaction liquid.

A 50-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 1.090 g (8 mmol) of zinc chloride and 4 ml of N-methylpyrrolidinone were weighed in the flask. The flask was purged with argon, followed by stirring. 3.5 ml (7 mmol) of 2M tetrahydrofuran solution of n-heptylmagnesium chloride was added dropwise at 25° C. over a period of 30 minutes, followed by stirring at 25° C. for 30 minutes. The reaction liquid previously obtained was added, followed by stirring at 25° C. for 30 minutes. Further, 0.558 g (5 mmol) of chlorobenzene was added, followed by stirring at 120° C. for 16 hours. After the completion of the reaction, 10 ml of toluene and 10 ml of saturated aqueous ammonium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.684 g of 1-phenylheptane (yield: 78 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Example A-11 Synthesis of 2-methylbiphenyl from 2-chlorotoluene and tri-n-butylphenyltin Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.045 g (0.2 mmol) of palladium (II) acetate, 1.337 g (8.8 mmol) of cesium fluoride and 4 ml of 1,4-dioxane were weighed in the flask, followed by stirring. Further, 0.418 g (0.8 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.506 g (4 mmol) of 2-chlorotoluene and 1.391 g (4.2 mmol) of tri-n-butylphenyltin were added, followed by stirring at 95° C. for 18 hours. After the completion of the reaction, 10 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.508 g of 2-methylbiphenyl (yield: 76 mol % based on 2-chlorotoluene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 168 (M⁺)

Example A-12 Synthesis of 2-methylbiphenyl from 2-bromotoluene and tri-n-butylphenyltin Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.045 g (0.2 mmol) of palladium (II) acetate, 1.337 g (8.8 mmol) of cesium fluoride and 4 ml of N-methylpyrrolidinone were weighed in the flask, followed by stirring. Further, 0.418 g (0.8 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.684 g (4 mmol) of 2-bromotoluene and 1.391 g (4.2 mmol) of tri-n-butylphenyltin were added, followed by stirring at 40° C. for 17 hours. After the completion of the reaction, 10 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.495 g of 2-methylbiphenyl (yield: 74 mol % based on 2-bromotoluene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 168 (M⁺)

Example A-13 Synthesis of (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester from 4-dimethylaminobromobenzene and methyl methacrylate Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 1.000 g (5 mmol) of 4-dimethylaminobromobenzene, 1.001 g (10 mmol) of methyl methacrylate, 0.011 g (0.012 mmol) of tris (dibenzylideneacetone)dipalladium (0), 1.074 g (5.5mmol) of dicyclohexylmethylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 25 hours. After the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.951 g of (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester (yield: 87 mol % based on 4-dimethylaminobromobenzene). The identification of the product was made by ¹H-NMR and ¹³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 2.15 ppm (s, 3H, H₃C—C) 2.98 ppm (s, 6H, H₃CN) 3.78 ppm (s, 3H, H₃CO) 6.69 ppm (d, J=8.8 Hz, 2H, ring proton) 7.37 ppm (d, J=8.8 Hz, 2H, ring proton) 7.62 ppm (s, 1H, HC═)

(2) ¹³C-NMR spectrum (δ in CDCl₃) 14.2, 40.1, 51.8, 111.6, 123.1, 123.7, 131.6, 139.4, 150.3, 169.8 ppm

Example A-14 Synthesis of (trans)-4-acetylstilbene from 4′-chloroacetophenone and styrene Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.773 g (5 mmol) of 4′-chloroacetophenone, 1.042 g (10 mmol) of styrene, 0.034 g (0.038 mmol) of tris(dibenzylideneacetone)dipalladium (0), 1.074 g (5.5 mmol) of dicyclohexylmethylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.078 g (0.15 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 37 hours. After the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.834 g of (trans)-4-acetylstilbene (yield: 75 mol % based on 4′-chloroacetophenone). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 222 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 2.60 ppm (s, 3H, H₃C) 7.11 ppm (d, J=16.5 Hz, 1H, HC═) 7.22 ppm (d, J=16.5 Hz, 1H, HC═) 7.24-40 ppm (m, 3H, ring proton) 7.53 ppm (d, J=7.2 Hz, 2H, ring proton) 7.57 ppm (d, J=8.7 Hz, 2H, ring proton) 7.94 ppm (d, J=8.7 Hz, 2H, ring proton)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 26.9, 126.6, 126.9, 127.5, 128.4, 128.9, 129.0, 131.5, 136.0, 136.8, 142.1, 197.5 ppm

Example A-15 Synthesis of (E)-3-(2,6-dimethylphenyl)-2-methylacrylic acid methyl ester from 2-chloro-meta-xylene and methyl methacrylate Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.703 g (5 mmol) of 2-chloro-meta-xylene, 1.001 g (10 mmol) of methyl methacrylate, 0.034 g (0.038 mmol) of tris(dibenzylideneacetone)dipalladium (0), 1.074 g (5.5 mmol) of dicyclohexylmethylamine and 5 ml of 1,4-dioxane were weighed in the flask, followed by stirring. Further, 0.078 g (0.15 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 120° C. for 37 hours. After the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.774 g of (E)-3-(2,6-dimethylphenyl)-2-methylacrylic acid methyl ester (yield: 76 mol % based on 2-chloro-meta-xylene). The identification of the product was made by ¹H-NMR and ¹³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 1.71 ppm (d, J=1.1 Hz, 3H, H₃C—C═) 2.18 ppm (s, 6H, H₃C) 3.84 ppm (s, 3H, H₃CO) 7.00-7.15 ppm (m, 3H, ring proton) 7.66 ppm (s, 1H, HC═)

(2) ¹³C-NMR spectrum (δ in CDCl₃) 13.6, 19.9, 51.8, 127.2, 127.3, 130.3, 135.0, 135.2, 139.0, 168.2 ppm

Example A-16 Synthesis of diphenylacetylene from bromobenzene and phenylacetylene Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 0.019 g (0.1 mmol) of copper (I) iodide, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.785 g (5 mmol) of bromobenzene and 1.021 g (10 mmol) of phenylacetylene were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.880 g of diphenylacetylene (yield: 99 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 178 (M⁺)

Example A-17 Synthesis of diphenylacetylene from bromobenzene and phenylacetylene Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.785 g (5 mmol) of bromobenzene and 0.613 g (6 mmol) of phenylacetylene were added, followed by stirring at 30° C. for 14 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.840 g of diphenylacetylene (yield: 94 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 178 (M⁺)

Example A-18 Synthesis of 4-[(trimethylsilyl)ethynyl]benzaldehyde from 4-bromobenzaldehyde and trimethylsilylacetylene Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 0.019 g (0.1 mmol) of copper (I) iodide, 1.088 g (6 mmol) of dicyclohexylamine and 9 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.925 g (5 mmol) of 4-bromobenzaldehyde and 0.589 g (6 mmol) of trimethylsilylacetylene were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.893 g of 4-[(trimethylsilyl)ethynyl]benzaldehyde (yield: 88 mol % based on 4-bromobenzaldehyde). The identification of the product was made by ¹H-NMR and ¹³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 0.26 ppm (s, 9H, H₃C) 7.59 ppm (d, J=8.1 Hz, 2H, ring proton) 7.81 ppm (d, J=8.1 Hz, 2H, ring proton) 9.99 ppm (s, 1H, HC)

(2) ¹³C-NMR spectrum (δ in CDCl₃) −0.2, 99.0, 103.8, 129.3, 129.4, 132.5, 135.6, 191.4 ppm

Example A-19 Synthesis of 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol from 4-bromo-N,N-dimethylaniline and 2-methyl-3-butyne-2-ol Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 0.019 g (0.1 mmol) of copper (I) iodide, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 1.000 g (5 mmol) of 4-bromo-N,N-dimethylaniline and 0.505 g (6 mmol) of 2-methyl-3-butyne-2-ol were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.876 g of 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol (yield: 86 mol % based on 4-bromo-N,N-dimethylaniline). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 203 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 1.58 ppm (s, 6H, H₃CC) 2.86 ppm (s, 6H, H₃CN) 3.38 ppm (s, 1H, HO) 6.54 ppm (d, J=9.0 Hz, 2H, ring proton) 7.76 ppm (d, J=9.0 Hz, 2H, ring proton)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 31.4, 39.8, 65.0, 82.4, 91.6, 109.6, 111.6, 132.3, 149.7 ppm

Example A-20 Synthesis of (4-fluorophenyl)-2-methyl-3-butyne-2-ol from 1-bromo-4-fluorobenzene and 2-methyl-3-butyne-2-ol Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.875 g (5 mmol) of 1-bromo-4-fluorobenzene and 0.505 g (6 mmol) of 2-methyl-3-butyne-2-ol were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.864 g of (4-fluorophenyl)-2-methyl-3-butyne-2-ol (yield: 97 mol % based on 1-bromo-4-fluorobenzene). The identification of the product was made by ¹H-NMR and ¹³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 1.59 ppm (s, 6H, H₃C) 3.41 ppm (s, 1H, HO) 6.88-6.95 ppm (m, 2H, ring proton) 7.30-7.36 ppm (m, 2H, ring proton)

(2) ¹³C-NMR spectrum (δ in CDCl₃) 31.5, 65.3, 80.8, 93.6, 115.3 (d, J=21.8 Hz), 122.1 (d, J=492.3 Hz), 133.3 (d, J=8.7 Hz), 162.2 (d, J=249.2 Hz) ppm

Example A-21 Synthesis of 1,2-diphenyl-1-propanone from chlorobenzene and propiophenone Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate, 0.721 g (7.5 mmol) of sodium-tert-butoxide and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.052 g (0.1 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 22° C. for 30 minutes. 0.563 g (5 mmol) of chlorobenzene was added, followed by stirring at 22° C. for 30 minutes. 0.738 g (5.5 mmol) of propiophenone was added, followed by stirring at 70° C. for 6 hours. After the completion of the reaction, 2.5 ml of water was added, followed by separation. The organic phase was purified by column chromatography to afford 0.814 g of 1,2-diphenyl-1-propanone (yield: 77 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 210 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 1.54 ppm (d, J=6.8 Hz, 3H, H₃C) 4.70 ppm (q, J=6.8 Hz, 1H, HC) 7.17-7.23 ppm (m, 1H, Ph) 7.29-7.30 ppm (m, 4H, Ph) 7.37-7.40 ppm (m, 2H, Ph) 7.48 ppm (t, J=7.3 Hz, 1H, Ph) 7.95 ppm (d, J=7.3 Hz, 2H, Ph)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 19.6, 47.9, 127.0, 127.8, 128.5, 128.8, 129.0, 132.3, 136.5, 141.6, 200.3 ppm

Example A-22 Synthesis of 1,2-diphenyl-1-propanone from bromobenzene and propiophenone Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.011 g (0.05 mmol) of palladium (II) acetate, 1.442 g (15 mmol) of sodium-tert-butoxide and 10 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 1.570 g (10 mmol) of bromobenzene was added, followed by stirring at 25° C. for 30 minutes. 1.476 g (11 mmol) of propiophenone was added, followed by stirring at 25° C. for 17 hours. After the completion of the reaction, 5 ml of water was added, followed by separation. The organic phase was purified by column chromatography to afford 2.065 g of 1,2-diphenyl-1-propanone (yield: 98 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 210 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 1.54 ppm (d, J=6.8 Hz, 3H, H₃C) 4.70 ppm (q, J=6.8 Hz, 1H, HC) 7.17-7.23 ppm (m, 1H, Ph) 7.29-7.30 ppm (m, 4H, Ph) 7.37-7.40 ppm (m, 2H, Ph) 7.48 ppm (t, J=7.3 Hz, 1H, Ph) 7.95 ppm (d, J=7.3 Hz, 2H, Ph)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 19.6, 47.9, 127.0, 127.8, 128.5, 128.8, 129.0, 132.3, 136.5, 141.6, 200.3 ppm

Example A-23 Synthesis of di-tert-butylphenyl malonate from chlorobenzene and di-tert-butyl malonate Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.013 g (0.06 mmol) of palladium (II) acetate, 0.317 g (3.3 mmol) of sodium-tert-butoxide and 9 ml of dioxane were weighed in the flask, followed by stirring. Further, 0.031 g (0.06 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.338 g (3 mmol) of chlorobenzene was added, followed by stirring at 25° C. for 30 minutes. 0.714 g (3.3 mmol) of di-tert-butyl malonate was added, followed by stirring at 100° C. for 12 hours. After the completion of the reaction, 9 ml of tetrahydrofuran and 9 ml of water were added, followed by separation. The organic phase was purified by column chromatography to afford 0.745 g of di-tert-butylphenyl malonate (yield: 85 mol % based on chlorobenzene). The identification of the product was made by ¹H-NMR and ¹³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 1.47 ppm (s, 18H, H₃C) 4.44 ppm (s, 1H, HC) 7.33-7.40 ppm (m, 5H, Ph)

(2) ¹³C-NMR spectrum (δ in CDCl₃) 27.9, 60.1, 81.9, 127.8, 128.4, 129.3, 133.5, 167.4 ppm

Example A-24 Synthesis of ethyl-2-phenylcyanoacetate from chlorobenzene and ethyl cyanoacetate Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate, 2.459 g (15 mmol) of sodium phosphate and 15 ml of toluene were weighed in the flask, followed by stirring. Further, 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.563 g (5 mmol) of chlorobenzene was added, followed by stirring at 25° C. for 30 minutes. 0.622 g (5.5 mmol) of ethyl cyanoacetate was added, followed by stirring at 100° C. for 12 hours. After the completion of the reaction, 5 ml of water was added, followed by separation. The organic phase was purified by column chromatography to afford 0.501 g of ethyl-2-phenylcyanoacetate (yield: 53 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 189 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 1.29 ppm (t, J=7.2 Hz, 3H, H₃C) 4.21-4.29 ppm (m, 2H, H₂C) 4.73 ppm (s, 1H, HC) 7.42-7.49 ppm (m, 5H, Ph)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 13.9, 43.7, 63.3, 115.7, 127.9, 129.2, 129.3, 130.0, 165.0 ppm

Example A-25 Synthesis of triphenylamine from chlorobenzene and diphenylamine Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 5.403 g (48 mmol) of chlorobenzene, 6.769 g (40 mmol) of diphenylamine, 4.613 g (48 mmol) of sodium-tert-butoxide, 0.002 g (0.01 mmol) of palladium (II) acetate and 5 ml of xylene were weighed in the flask, followed by stirring. Further, 0.021 g (0.04 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 100-120° C. for 10 hours. After the completion of the reaction, 45 ml of xylene and 50 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 9.008 g of triphenylamine (yield: 92 mol % based on diphenylamine). The melting point was 125-126° C.

Example A-26 Synthesis of tert-butyl-2-methylphenyl ether from 2-chlorotoluene and sodium-tert-butoxide Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 6.330 g (50 mmol) of 2-chlorotoluene, 5.766 g (60 mmol) of sodium-tert-butoxide, 0.112 g (0.5 mmol) of palladium (II) acetate and 50 ml of xylene were weighed in the flask, followed by stirring. Further, 0.784 g (1.5 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 125° C. for 3 hours. After the completion of the reaction, 10 ml of water was added, followed by separation. The organic phase was purified by distillation to afford 7.695 g of tert-butyl-2-methylphenyl ether (yield: 94 mol % based on 2-chlorotoluene). The boiling point was 75° C./9 Torr.

Example A-27 Synthesis of 2-methoxy-4,2′-dimethylphenyl ether from 2-chlorotoluene and 2-methoxy-4-methylphenol Synthesis in which tri-tert-butylphosphonium tetraphenylborate was handled in air

A 200-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 1.920 g (48 mmol) of 60 wt % sodium hydride and 50 ml of toluene were weighed in the flask. The flask was purged with argon, followed by stirring. 6.632 g (48 mmol) of 2-methoxy-4-methylphenol was added, followed by stirring at 25° C. for 30 minutes. Further, 5.064 g (40 mmol) of 2-chlorotoluene and 0.449 g (2 mmol) of palladium (II) acetate were added, followed by stirring. Further, 1.045 g (2 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask, followed by stirring at 104° C. for 9 hours. After the completion of the reaction, 50 ml of saturated sodium chloride solution was added, followed by separation. The organic phase was purified by column chromatography to afford 6.803 g of 2-methoxy-4,2′-dimethylphenyl ether (yield: 75 mol % based on 2-chlorotoluene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 228 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 2.32 ppm (s, 3H, H₃C) 2.34 ppm (s, 3H, H₃C) 3.84 ppm (s, 3H, H₃CO) 6.68-6.81 ppm (m, 4H, ring proton) 6.95-7.22 ppm (m, 3H, ring proton)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 16.2, 21.2, 56.0, 113.7, 117.1, 117.2, 119.3, 121.3, 122.8, 126.8, 131.1, 133.7, 143.8, 150.5, 155.8 ppm

Example B-1 Production of di-tert-butylmethylphosphonium tetraphenylborate

A 30-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. 6.4 g (40 mmol) of di-tert-butylmethylphosphine and 6.4 ml of heptane were weighed in the flask, followed by stirring to dissolve di-tert-butylmethylphosphine. While the stirring was continuously carried out, 8.0 ml (40 mmol) of 5N hydrochloric acid was added to the solution, and the mixture was stirred at 25° C. for 1 hour. Thereafter, the organic phase was analyzed by gas chromatography, which confirmed the disappearance of di-tert-butylmethylphosphine. After the completion of the reaction, the liquid was separated. The aqueous phase was washed with 6.4 ml of heptane. The aqueous phase was assumed to contain di-tert-butylmethylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 15.1 g (44 mmol) of sodium tetraphenylborate and 60 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of di-tert-butylmethylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 17.1 g of objective di-tert-butylmethylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 89% based on di-tert-butylmethylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be di-tert-butylmethylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 192-196° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.33 ppm (d, 18H, J=16.7 Hz, H₃C—C—P) 1.83 ppm (d, 3H, J=13.6 Hz, H₃C—P) 5.27-7.18 ppm (brd, 1H, H—P) 6.80 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.93 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.20 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) −3.2 ppm (d, J=43.5 Hz, H₃C—P) 26.0 ppm (s, H₃C—C—P) 30.8 ppm (d, J=37.9 Hz, H₃C—C—P) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=2.5 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.9 Hz, Ph-B) 163.3 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

Example B-2 Production of di-tert-butylmethylphosphonium tetra-para-tolylborate

A30-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. 6.4 g (40 mmol) of di-tert-butylmethylphosphine and 6.4 ml of heptane were weighed in the flask, followed by stirring to dissolve di-tert-butylmethylphosphine. While the stirring was continuously carried out, 11.0 ml (22 mmol) of 4N sulfuric acid was added to the solution, and the mixture was stirred at 25° C. for 1 hour. Thereafter, the organic phase was analyzed by gas chromatography, which confirmed the disappearance of di-tert-butylmethylphosphine. After the completion of the reaction, the liquid was separated. The aqueous phase was washed with 6.4 ml of heptane. The aqueous phase was assumed to contain di-tert-butylmethylphosphine sulfate dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 19.1 g (48 mmol) of sodium tetra-para-tolylborate, 100 ml of tetrahydrofuran and 100 ml of toluene were weighed in the flask, followed by stirring to dissolve sodium tetra-para-tolylborate. While the stirring was continuously carried out, the aqueous solution of di-tert-butylmethylphosphine sulfate previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off and washed with 200 ml of toluene. The so obtained crystal was suspended in 200 ml of water at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 200 ml of water. The crystal was then suspended in 200 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 200 ml of methanol. The crystal obtained was dried to give 17.2 g of objective di-tert-butylmethylphosphonium tetra-para-tolylborate as white crystal. The yield (mol %) was 80% based on di-tert-butylmethylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be di-tert-butylmethylphosphonium tetra-para-tolylborate. The analytical values and properties were as follows.

(1) Melting point: 157-166° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.32 ppm (d, 18H, J=16.5 Hz, H₃C—C—P) 1.81 ppm (d, 3H, J=13.6 Hz, H₃C—P) 2.15 ppm (s, 12H, H₃C—C₆H₄—B) 5.18-7.08 ppm (brd, 1H, H—P) 6.72 ppm (t, 8H, J=7.70 Hz, H₃C—C₆H₄—B) 7.05 ppm (brs, 8H, H₃C—C₆H₄—B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 3.2 ppm (d, J=45.4 Hz, H₃C—P) 20.8 ppm (s, H₃C—C₆H₄—B) 26.1 ppm (s, H₃C—C—P) 30.8 ppm (d, J=37.9 Hz, H₃C—C—P) 126.0 ppm (dd, J=2.5 Hz, 5.6 Hz, H₃C—C₆H₄—B) 129.0 ppm (s, H₃C—C₆H₄quaternary-B) 135.5 ppm (d, J=1.2 Hz, H₃C—C₆H₄—B) 160.2 ppm (dd, J=49.7 Hz, 98.8 Hz, H₃C—C₆H₄quaternary-B)

Example B-3 Production of tri-tert-butylphosphonium tetra-para-tolylborate

The procedures in Example B-2 were repeated except that 6.4 g (40 mmol) of di-tert-butylmethylphosphine was replaced with 8.1 g (40 mmol) of tri-tert-butylphosphine. Consequently, 19.0 g of objective tri-tert-butylphosphonium tetra-para-tolylborate was obtained as white crystal. The yield (mol %) was 82% based on tri-tert-butylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be tri-tert-butylphosphonium tetra-para-tolylborate. The analytical values and properties were as follows.

(1) Melting point: 179-201° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.49 ppm (d, 27H, J=15.2 Hz, H₃C—C—P) 2.15 ppm (s, 12H, H₃C—C₆H₄—B) 5.23-7.07 ppm (brd, 1H, H—P) 6.72 ppm (t, 8H, J=7.70 Hz, H₃C—C₆H₄—B) 7.05 ppm (brs, 8H, H₃C—C₆H₄—B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 20.8 ppm (s, H₃C—C₆H₄—B) 29.3 ppm (s, H₃C—C—P) 36.3 ppm (d, J=28.6 Hz, H₃C—C—P) 125.9 ppm (dd, J=2.5 Hz, 5.6 Hz, H₃C—C₆H₄—B) 129.0 ppm (s, H₃C—C₆H₄quaternary-B) 135.5 ppm (s, H₃C—C₆H₄—B) 160.2 ppm (dd, J=49.7 Hz, 99.4 Hz, H₃C—C₆H₄quaternary-B)

Example B-4 Production of di-tert-butylethylphosphonium tetraphenylborate

The procedures in Example B-1 were repeated except that 6.4 g (40 mmol) of di-tert-butylmethylphosphine was replaced with 7.0 g (40 mmol) of di-tert-butylethylphosphine. Consequently, 15.8 g of objective di-tert-butylethylphosphonium tetraphenylborate was obtained as white crystal. The yield (mol %) was 80% based on di-tert-butylethylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be di-tert-butylethylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 174-188° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.30 ppm (dt, 3H, J=18.7, 7.70 Hz, H₃C—CH₂—P) 1.38 ppm (d, 18H, J=16.1 Hz, H₃C—C—P) 2.33-2.39 ppm (m, 2H, H₃C—CH₂—P) 5.92 ppm (brd, 1H, J=466.6 Hz, H—P) 6.79 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.93 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.19 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 7.0 ppm (d, J=41.0 Hz, H₃C—CH₂—P) 11.0 ppm (d, J=6.2 Hz, H₃C—CH₂—P) 26.3 ppm (s, H₃C—C—P) 32.2 ppm (d, J=35.4 Hz, H₃C—C—P) 121.5 ppm (s, Ph-B) 125.2 ppm (dd, J=3.1 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.5 Hz, 98.5 Hz, Ph quaternary-B)

Production of n-butyl-di-tert-butylphosphonium tetraphenylborate

The procedures in Example B-1 were repeated except that 6.4 g (40 mmol) of di-tert-butylmethylphosphine was replaced with 8.1 g (40 mmol) of n-butyl-di-tert-butylphosphine. Consequently, 15.9 g of objective n-butyl-di-tert-butylphosphonium tetraphenylborate was obtained as white crystal. The yield (mol %) was 76% based on n-butyl-di-tert-butylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be n-butyl-di-tert-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 156-162° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 0.93 ppm (t, 3H, J=7.34 Hz, H₃C—CH₂—CH₂—CH₂—P) 1.40 ppm (d, 18H, J=16.1 Hz, H₃C—C—P) 1.43-1.51 ppm (m, 2H, H₃C—CH₂—CH₂—CH₂—P) 1.59-1.61 ppm (m, 2H, H₃C—CH₂—CH₂—CH₂—P) 2.28-2.38 ppm (m, 2H, H₃C—CH₂—CH₂—CH₂—P) 5.21-7.18 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.18 ppm (brs, 8H, Ph-B)

(4) 1³C-NMR spectrum (δ in DMSO-d6) 12.8 ppm (d, J=40.4 Hz, H₃C—CH₂—CH₂—CH₂—P) 13.2 ppm (s, H₃C—CH₂—CH₂—CH₂—P) 23.0 ppm (d, J=13.1 Hz, H₃C—CH₂—CH₂—CH₂—P) 26.3 ppm (s, H₃C—C—P) 28.5 ppm (d, J=5.6 Hz, H₃C—CH₂—CH₂—CH₂—P) 32.1 ppm (d, J=35.4 Hz, H₃C—C—P) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=2.5 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, HPh-B) 163.4 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

Example B-6 Production of sec-butyl-di-tert-butylphosphonium tetraphenylborate

A 100-ml four-necked flask sufficiently purged with nitrogen was equipped with a stirrer, a thermometer and a reflux condenser. 7.2 g (40 mmol) of di-tert-butylphosphinas chloride, 0.040 g (0.40 mmol) of copper (I) chloride and 7.2 ml of tetrahydrofuran were weighed in the flask. A sec-butylmagnesium chloride solution was added dropwise to the flask at an internal temperature of 10-20° C. over a period of 1 hour, wherein the solution had been previously prepared from 4.8 g (52 mmol) of sec-butyl chloride and 1.3 g (52 mmol) of metallic magnesium in 20 g of tetrahydrofuran. The mixture was stirred at 20-30° C. for 2 hours. Gas chromatography analysis confirmed the disappearance of di-tert-butylphosphinas chloride. After the completion of the reaction, 26 ml of toluene was added, and 11.8 g (6 mmol) of 5% sulfuric acid was added dropwise to dissolve the magnesium salt, followed by separation. The organic phase was washed with 11.8 ml of water.

A 100-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. The solution of sec-butyl-di-tert-butylphosphine prepared above was weighed in the flask, to which 8.0 ml (40 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of sec-butyl-di-tert-butylphosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 8.0 ml of heptane. The aqueous phase was assumed to contain sec-butyl-di-tert-butylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 15.1 g (44 mmol) of sodium tetraphenylborate and 60 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of sec-butyl-di-tert-butylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 15.7 g of objective sec-butyl-di-tert-butylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 75% based on di-tert-butylphosphinas chloride.

The crystal was analyzed by the methods indicated below and was identified to be sec-butyl-di-tert-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 184-187° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.03 ppm (t, 3H, J=7.34 Hz, H₃C—CH₂—CH—P) 1.38-1.44 ppm (m, 3H, H₃C—CH—P) 1.41 ppm (d, 9H, J=16.0 Hz, H₃C—C—P) 1.45 ppm (d, 9H, J=15.8 Hz, H₃C—C—P) 1.64-1.78 ppm (m, 1H, H₃C—CH₂—CH—P) 1.81-1.93 ppm (m, 1H, H₃C—CH₂—CH—P) 2.73-2.76 ppm (m, 1H, H₃C—CH₂—CH—P) 5.22-7.19 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.14 Hz, Ph-B) 6.93 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.19 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 12.3 ppm (d, J=11.2 Hz, H₃C—CH—P) 15.2 ppm (d, J=2.5 Hz, H₃C—CH₂—CH—P) 26.5 ppm (s, H₃C—CH₂—CH—P) 27.1 ppm (d, J=34.9 Hz, H₃C—CH₂—CH—P) 27.4 ppm (s, H₃C—C—P) 27.8 ppm (s, H₃C—C—P) 33.8 ppm (d, J=32.3 Hz, H₃C—C—P) 34.2 ppm (d, J=31.1 Hz, H₃C—C—P) 121.5 ppm (s, Ph-B) 125.2 ppm (dd, J=3.1 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

Example B-7 Production of cyclohexyl-di-tert-butylphosphonium tetraphenylborate

A 100-ml four-necked flask sufficiently purged with nitrogen was equipped with a stirrer, a thermometer and a reflux condenser. 7.2 g (40 mmol) of di-tert-butylphosphinas chloride, 0.040 g (0.40 mmol) of copper (I) chloride and 7.2 ml of tetrahydrofuran were weighed in the flask. A cyclohexyl magnesium chloride solution was added dropwise to the flask at an internal temperature of 10-20° C. over a period of 1 hour, wherein the solution had been previously prepared from 6.2 g (52 mmol) of cyclohexyl chloride and 1.3 g (52 mmol) of metallic magnesium in 19 g of tetrahydrofuran. The mixture was stirred at 20-30° C. for 2 hours. Gas chromatography analysis confirmed the disappearance of di-tert-butylphosphinas chloride. After the completion of the reaction, 26 ml of toluene was added, and 11.8 g (6 mmol) of 5% sulfuric acid was added dropwise to dissolve the magnesium salt, followed by separation. The organic phase was washed with 11.8 ml of water.

A 100-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. The solution of cyclohexyl-di-tert-butylphosphine prepared above was weighed in the flask, to which 8.8 ml (44 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of cyclohexyl-di-tert-butylphosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 8.8 ml of heptane. The aqueous phase was assumed to contain cyclohexyl-di-tert-butylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 16.4 g (48 mmol) of sodium tetraphenylborate and 66 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of cyclohexyl-di-tert-butylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 15.8 g of objective cyclohexyl-di-tert-butylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 72% based on di-tert-butylphosphinas chloride.

The crystal was analyzed by the methods indicated below and was identified to be cyclohexyl-di-tert-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 171-178° C. (decomposition temperature)

(2) IR spectrum (KBr) 2390 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.16-1.35 ppm (m, 3H, cyclohexyl secondary) 1.38 ppm (d, 18H, J=15.8 Hz, H₃C—C—P) 1.62-1.75 ppm (m, 5H, cyclohexyl secondary) 1.83-2.03 ppm (m, 2H, cyclohexyl secondary) 2.60-2.72 ppm (m, 1H, cyclohexyl tertiary) 5.75 ppm (brd, 1H, J=462.3 Hz, H_—P)6.80 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.94 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.22 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 24.7 ppm (d, J=1.2 Hz, cyclohexyl secondary) 26.2 ppm (d, J=11.8 Hz, cyclohexyl secondary) 27.6 ppm (s, H₃HC—C—P) 28.9 ppm (d, J=3.7 Hz, cyclohexyl secondary) 30.8 ppm (d, J=34.2 Hz, cyclohexyl tertiary) 34.0 ppm (d, J=31.7 Hz, H₃C—HC—P) 121.5 ppm (s, Ph-B) 125.3 ppm (dd, J=2.5 Hz, 5.6 Hz, Ph-B) 135.6 ppm (d, J=1.2 Hz, Ph-B) 163.4 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

Example B-8 Production of di-tert-butyl-n-octylphosphonium tetraphenylborate

A 100-ml four-necked flask sufficiently purged with nitrogen was equipped with a stirrer, a thermometer and a reflux condenser. 7.2 g (40 mmol) of di-tert-butylphosphinas chloride, 0.040 g (0.40 mmol) of copper (I) chloride and 7.2 ml of tetrahydrofuran were weighed in the flask. A n-octylmagnesium chloride solution was added dropwise to the flask at an internal temperature of 10-20° C. over a period of 1 hour, wherein the solution had been previously prepared from 7.7 g (52 mmol) of n-octyl chloride and 1.3 g (52 mmol) of metallic magnesium in 17 g of tetrahydrofuran. The mixture was stirred at 20-30° C. for 2 hours. Gas chromatography analysis confirmed the disappearance of di-tert-butylphosphinas chloride. After the completion of the reaction, 26 ml of toluene was added, and 11.8 g (6 mmol) of 5% sulfuric acid was added dropwise to dissolve the magnesium salt, followed by separation. The organic phase was washed with 11.8 ml of water.

A 100-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. The solution of di-tert-butyl-n-octylphosphine prepared above was weighed in the flask, to which 8.8 ml (44 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of di-tert-butyl-n-octylphosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 8.8 ml of heptane. The aqueous phase was assumed to contain di-tert-butyl-n-octylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 16.4 g (48 mmol) of sodium tetraphenylborate and 66 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of di-tert-butyl-n-octylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 17.4 g of objective di-tert-butyl-n-octylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 75% based on di-tert-butylphosphinas chloride.

The crystal was analyzed by the methods indicated below and was identified to be di-tert-butyl-n-octylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 108-113° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 0.86 ppm (t, 3H, J=5.87 Hz, H₃C—(CH)₅—CH₂—CH₂—P) 1.27 ppm (brs, 10H, H₃C—(CH₂)₅—CH₂—CH₂—P) 1.39 ppm (d, 18H, J=16.1 Hz, H₃C—C—P) 1.60-1.71 ppm (m, 2H, H₃C—(CH₂)₅—CH₂—CH₂—P) 2.25-2.35 ppm (m, 2H, H₃C—(CH₂)₅—CH₂—CH₂—P) 5.20-7.19 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.25 Hz, Ph-B) 7.19 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 13.8 ppm (d, J=40.0 Hz, H₃C—(CH₂)₆—CH₂—P) 13.9 ppm (s, H₃C—CH₂—CH₂—CH₂—P) 22.0 ppm (s, H₃C—(PH₂)₄—(CH₂)₃—P) 26.3 ppm (s, H₃C—C—P) 26.5 ppm (d, J=6.2 Hz, H₃C—(CH₂)₄—CH₂—(CH₂)₂—P) 28.2 ppm (s, H₃C—(CH₂)₄—(CH₂)₃—P) 28.4 ppm (s, H₃C—(CH₂)₄—(CH₂)₃—P) 29.8 ppm (d, J=11.8 Hz, H₃C—(CH₂)₅—CH₂—CH₂—P) 31.1 ppm (s, H₃C—(CH₂)₄—(CH₂)₃—P) 32.1 ppm (d, J=35.4 Hz, H₃C—C—P) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=2.5 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.0 Hz, 98.5 Hz, Ph quaternary-B)

Example B-9 Production of di-tert-butylphenylphosphonium tetraphenylborate

The procedures in Example B-1 were repeated except that 6.4 g (40 mmol) of di-tert-butylmethylphosphine was replaced with 8.9 g (40 mmol) of di-tert-butylphenylphosphine. Consequently, 17.8 g of objective di-tert-butylphenylphosphonium tetraphenylborate was obtained as white crystal. The yield (mol %) was 82% based on di-tert-butylphenylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be di-tert-butylphenylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 135-140° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.40 ppm (d, 18H, J=16.7 Hz, H₃C—C—P) 6.76-7.95 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.54 Hz, Ph-B) 7.19 ppm (brs, 8H, Ph-B) 7.70 ppm (t, 2H, J=7.70 Hz, Ph-P) 7.83 ppm (t, 1H, J=7.89 Hz, Ph-P) 7.92 ppm (t, 2H, J=7.89 Hz, Ph-P)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 27.0 ppm (s, H₃C—C—P) 33.3 ppm (d, J=31.7 Hz, H₃C—C—P) 121.5 ppm (s, Ph-B) 125.3 ppm (dd, J=3.1 Hz, 5.6 Hz, Ph-B) 126.6 ppm (s, Ph-P) 128.3 ppm (s, Ph quaternary-P) 130.0 ppm (d, J=11.2 Hz, Ph-P) 133.3 ppm (s, Ph-P) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.4 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

Example B-10 Production of 2-biphenylyl-di-tert-butylphosphonium tetraphenylborate

A 50-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. 11.9 g (40 mmol) of 2-biphenylyl-di-tert-butylphosphine and 11.9 ml of heptane were weighed in the flask, followed by stirring to dissolve 2-biphenylyl-di-tert-butylphosphine. While the stirring was continuously carried out, 12.0 ml (60 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of 2-biphenylyl-di-tert-butylphosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 11.9 ml of heptane. The aqueous phase was assumed to contain 2-biphenylyl-di-tert-butylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 22.6 g (66 mmol) of sodium tetraphenylborate and 90 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of 2-biphenylyl-di-tert-butylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 19.3 g of objective 2-biphenylyl-di-tert-butylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 78% based on 2-biphenylyl-di-tert-butylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be 2-biphenylyl-di-tert-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 163-174° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.26 ppm (d, 18H, J=17.1 Hz, H₃C—C—P) 6.77-7.96 ppm (brd, 1H, H—P) 6.80 ppm (t, 4H, J=7.06 Hz, Ph-B) 6.94 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.18-7.21 ppm (m, 2H, 2-biphenyl) 7.28 ppm (brs, 8H, Ph-B) 7.45-7.47 ppm (m, 4H, 2-biphenyl) 7.62 ppm (d, 1H, J=7.52 Hz, 2-biphenyl) 7.72 ppm (d, 1H, J=7.61 Hz, 2-biphenyl) 7.93 ppm (d, 1H, J=8.63 Hz, 2-biphenyl)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 27.3 ppm (s, H₃C—C—P) 34.2 ppm (d, J=30.5 Hz, H₃C—C—P) 121.5 ppm (s, Ph-B) 125.3 ppm (dd, J=2.5 Hz, 5.6 Hz, Ph-B) 126.5 ppm (s, 2-biphenyl) 128.2 ppm (s, 2-biphenyl) 128.6 ppm (s, 2-biphenyl) 128.8 ppm (s, 2-biphenyl) 129.3 ppm (s, 2-biphenyl) 132.2 ppm (d, J=8.1 Hz, 2-biphenyl) 133.0 ppm (d, J=17.4 Hz, 2-biphenyl) 134.0 ppm (s, 2-biphenyl quaternary) 135.6 ppm (s, Ph-B) 138.4 ppm (s, 2-biphenyl quaternary) 148.3 ppm (s, 2-biphenyl quaternary) 163.4 ppm (dd, J=49.7 Hz, 98.8 Hz, Ph quaternary-B)

Example B-11 Production of di-tert-butyl-1-naphthylphosphonium tetraphenylborate

The procedures in Example B-10 were repeated except that 11.9 g (40 mmol) of 2-biphenylyl-di-tert-butylphosphine was replaced with 10.9 g (40 mmol) of di-tert-butyl-1-naphthylphosphine. Consequently, 19.0 g of objective di-tert-butyl-1-naphthylphosphonium tetraphenylborate was obtained as white crystal. The yield (mol %) was 80% based on di-tert-butyl-1-naphthylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be di-tert-butyl-1-naphthylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 165-174° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.39 ppm (d, 18H, J=16.9 Hz, H₃C—C—P) 6.82-8.51 ppm (brd, 1H, H—P) 6.84 ppm (t, 4H, J=7.06 Hz, Ph-B) 6.99 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.35 ppm (brs, 8H, Ph-B) 7.65-7.82 ppm (m, 3H, 1-naphthyl) 8.10 ppm (d, 1H, J=8.07 Hz, 1-naphthyl) 8.13-8.19 ppm (m, 1H, 1-naphthyl) 8.32 ppm (d, 1H, J=8.25 Hz, 1-naphthyl) 8.50 ppm (d, 1H, J=8.62 Hz, 1-naphthyl)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 27.3 ppm (s, H₃C—C—P) 34.4 ppm (d, J=29.2 Hz, H₃C—C—P) 121.5 ppm (s, Ph-B) 124.1 ppm (d, J=9.9 Hz, 1-naphthyl) 125.1 ppm (s, 1-naphthyl) 125.3 ppm (dd, J=2.5 Hz, 5.6 Hz, Ph-B) 126.5 ppm (s, 1-naphthyl) 127.3 ppm (s, 1-naphthyl) 128.2 ppm (s, 1-naphthyl) 128.9 ppm (s, 1-naphthyl) 129.9 ppm (s, 1-naphthyl) 133.1 ppm (s, 1-naphthyl quaternary) 133.3 ppm (d, J=7.5 Hz, 1-naphthyl quaternary) 134.4 ppm (d, J=6.7 Hz, 1-naphthyl quaternary) 135.7 ppm (s, Ph-B) 163.5 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

Example B-12 Production of benzyl-di-tert-butylphosphonium tetraphenylborate

The procedures in Example B-1 were repeated except that 6.4 g (40 mmol) of di-tert-butylmethylphosphine was replaced with 9.5 g (40 mmol) of benzyl-di-tert-butylphosphine. Consequently, 18.0 g of objective benzyl-di-tert-butylphosphonium tetraphenylborate was obtained as white crystal. The yield (mol %) was 81% based on benzyl-di-tert-butylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be benzyl-di-tert-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 149-158° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.38 ppm (d, 18H, J=15.8 Hz, H₃C—C—P) 3.99 ppm (brs, 2H, Ph-CH₂—P) 6.76-7.44 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.18 ppm (brs, 8H, Ph-B) 7.32-7.44 ppm (m, 5H, Ph-CH₂—P)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 20.4 ppm (d, J=40.0 Hz, Ph-CH₂—P) 26.7 ppm (s, H₃C—C—P) 32.9 ppm (d, J=32.3 Hz, H₃C—C—P) 121.5 ppm (s, Ph-B) 125.2 ppm (dd, J=2.5 Hz, 5.6 Hz, Ph-B) 127.6 ppm (s, Ph-CH₂—P) 129.1 ppm (s, Ph-CH₂—P) 129.7 ppm (d, J=6.2 Hz, Ph-CH₂—P) 133.0 ppm (s, Ph quaternary-CH₂—P) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

Example B-13 Production of di-tert-butyl(4-ethenylbenzyl)phosphonium tetraphenylborate

A 100-ml four-necked flask sufficiently purged with nitrogen was equipped with a stirrer, a thermometer and a reflux condenser. 7.2 g (40 mmol) of di-tert-butylphosphinas chloride, 0.040 g (0.40 mmol) of copper (I) chloride and 7.2 ml of tetrahydrofuran were weighed in the flask. A 4-ethenylbenzylmagnesium chloride solution was added dropwise to the flask at an internal temperature of 10-20° C. over a period of 1 hour, wherein the solution had been previously prepared from 7.9 g (52 mmol) of 4-ethenylbenzyl chloride and 1.3 g (52 mmol) of metallic magnesium in 17 g of tetrahydrofuran. The mixture was stirred at 20-30° C. for 2 hours. Gas chromatography analysis confirmed the disappearance of di-tert-butylphosphinas chloride. After the completion of the reaction, 26 ml of toluene was added, and 11.8 g (6 mmol) of 5% sulfuric acid was added dropwise to dissolve the magnesium salt, followed by separation. The organic phase was washed with 11.8 ml of water.

A 100-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. The solution of di-tert-butyl(4-ethenylbenzyl)phosphine prepared above was weighed in the flask, to which 8.0 ml (40 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of di-tert-butyl(4-ethenylbenzyl)phosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 8.0 ml of heptane. The aqueous phase was assumed to contain di-tert-butyl(4-ethenylbenzyl)phosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 15.1 g (44 mmol) of sodium tetraphenylborate and 60 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of di-tert-butyl(4-ethenylbenzyl)phosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 17.7 g of objective di-tert-butyl(4-ethenylbenzyl)phosphonium tetraphenylborate as white crystal. The yield (mol %) was 76% based on di-tert-butylphosphinas chloride.

The crystal was analyzed by the methods indicated below and was identified to be di-tert-butyl(4-ethenylbenzyl)phosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 122-132° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.40 ppm (d, 18H, J=16.1 Hz, H₃C—C—P) 3.96 ppm (brs, 2H, H₂C═CH—C₆H₄—CH₂—P) 5.29 ppm (d, 1H, 11.0 Hz, H₂C═CH—C₆H₄—CH₂—P) 5.86 ppm (d, 1H, 17.8 Hz, H₂C═CH—C₆H₄—CH₂—P) 6.68-7.53 ppm (brd, 1H, H—P) 6.70 ppm (d, 1H, 10.8 Hz, H₂C═CH—C₆H₄—CH₂—P) 6.78 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.24 Hz, Ph-B) 7.18 ppm (brs, 8H, Ph-B) 7.42 ppm (d, 2H, J=7.70 Hz, H₂C═CH—C₆H₄—CH₂—P) 7.51 ppm (d, 2H, J=7.89 Hz, H₂C═CH—C₆H₄—CH₂—P)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 20.3 ppm (d, J=34.8 Hz, H₂C═CH—C₆H₄—CH₂—P) 26.7 ppm (s, H₃C—C—P) 32.8 ppm (d, J=31.7 Hz, H₃C—C—P) 114.9 ppm (s, H₂C═CH—C₆H₄—CH₂—P) 121.5 ppm (s, Ph-B) 125.2 ppm (dd, J=2.5 Hz, 5.0 Hz, Ph-B) 126.7 ppm (s, H₂C═CH—C₆H₄—CH₂—P) 128.1 ppm (d, J=6.8 Hz, H₂C═CH—C₆H₄quaternary-CH₂—P) 128.8 ppm (s, H₂C═CH—C₆H₄quaternary-CH₂—P) 129.9 ppm (s, H₂C═CH—C₆H₄—CH₂—P) 135.6 ppm (s, Ph-B) 135.8 ppm (s, H₂C═CH—C₆H₄—CH₂—P) 163.4 ppm (dd, J=49.4 Hz, 98.5 Hz, Ph quaternary-B)

Example B-14 Production of di-tert-butylvinylphosphonium tetraphenylborate

A 100-ml four-necked flask sufficiently purged with nitrogen was equipped with a stirrer, a thermometer and a reflux condenser. 7.2 g (40 mmol) of di-tert-butylphosphinas chloride, 0.040 g (0.40 mmol) of copper (I) chloride and 7.2 ml of tetrahydrofuran were weighed in the flask. A vinylmagnesium chloride solution was added dropwise to the flask at an internal temperature of 10-20° C. over a period of 1 hour, wherein the solution had been previously prepared from 3.3 g (52 mmol) of vinyl chloride and 1.3 g (52 mmol) of metallic magnesium in 21 g of tetrahydrofuran. The mixture was stirred at 40-50° C. for 2 hours. Gas chromatography analysis confirmed the disappearance of di-tert-butylphosphinas chloride. After the completion of the reaction, 26 ml of toluene was added, and 11.8 g (6 mmol) of 5% sulfuric acid was added dropwise to dissolve the magnesium salt, followed by separation. The organic phase was washed with 11.8 ml of water.

A 100-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. The solution of di-tert-butylvinylphosphine prepared above was weighed in the flask, to which 8.0 ml (40 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of di-tert-butylvinylphosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 8.0 ml of heptane. The aqueous phase was assumed to contain di-tert-butylvinylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 15.1 g (44 mmol) of sodium tetraphenylborate and 60 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of di-tert-butylvinylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 14.4 g of objective di-tert-butylvinylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 73% based on di-tert-butylphosphinas chloride.

The crystal was analyzed by the methods indicated below and was identified to be di-tert-butylvinylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 253-261° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

Example B-15 Production of allyl-di-tert-butylphosphonium tetraphenylborate

A 100-ml four-necked flask sufficiently purged with nitrogen was equipped with a stirrer, a thermometer and a reflux condenser. 7.2 g (40 mmol) of di-tert-butylphosphinas chloride, 0.040 g (0.40 mmol) of copper (I) chloride and 7.2 ml of tetrahydrofuran were weighed in the flask. An allylmagnesium chloride solution was added dropwise to the flask at an internal temperature of 10-20° C. over a period of 1 hour, wherein the solution had been previously prepared from 4.0 g (52 mmol) of allyl chloride and 1.3 g (52 mmol) of metallic magnesium in 21 g of tetrahydrofuran. The mixture was stirred at 20-30° C. for 1 hour. Gas chromatography analysis confirmed the disappearance of di-tert-butylphosphinas chloride. After the completion of the reaction, 26 ml of toluene was added, and 11.8 g (6 mmol) of 5% sulfuric acid was added dropwise to dissolve the magnesium salt, followed by separation. The organic phase was washed with 11.8 ml of water.

A 200-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. The solution of allyl-di-tert-butylphosphine prepared above was weighed in the flask, to which 8.0 ml (40 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of allyl-di-tert-butylphosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 8.0 ml of heptane. The aqueous phase was assumed to contain allyl-di-tert-butylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 15.1 g (44 mmol) of sodium tetraphenylborate and 60 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of allyl-di-tert-butylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 15.2 g of objective allyl-di-tert-butylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 75% based on di-tert-butylphosphinas chloride.

The crystal was analyzed by the methods indicated below and was identified to be allyl-di-tert-butylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 148-160° C. (decomposition temperature)

(2) IR spectrum (KBr) 2384 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.40 ppm (d, 18H, J=16.1 Hz, H₃C—C—P) 3.34 ppm (brs, 2H, H₂C═CH—CH₂—P) 5.33 ppm (d, 1H, 9.54 Hz, H₂C═CH—CH₂—P) 5.47 ppm (d, 1H, 16.3 Hz, H₂C═CH—CH₂—P) 5.84-5.97 ppm (m, 1H, H₂C═CH—CH₂—P) 6.77-7.36 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.06 Hz, Ph-B) 6.93 ppm (t, 8H, J=7.25 Hz, Ph-B) 7.18 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 18.7 ppm (d, J=36.7 Hz, H₂C═CH—CH₂—P) 26.6 ppm (s, H₃C—C—P) 32.6 ppm (d, J=32.3 Hz, H₃C—C—P) 109.5 ppm (s, H₂C═CH—CH₂—P) 115.2 ppm (s, H₂C═CH—CH₂—P) 121.5 ppm (s, Ph-B) 125.2 ppm (dd, J=2.5 Hz, 5.6 Hz, Ph-B) 135.5 ppm (s, Ph-B) 163.4 ppm (dd, J=49.7 Hz, 98.8 Hz, Ph quaternary-B)

Example B-16 Production of tricyclohexylphosphonium tetra-para-tolylborate

The procedures in Example B-2 were repeated except that 6.4 g (40 mmol) of di-tert-butylmethylphosphine was replaced with 11.2 g (40 mmol) of tricyclohexylphosphine. Consequently, 22.3 g of objective tricyclohexylphosphonium tetra-para-tolylborate was obtained as white crystal. The yield (mol %) was 85% based on tricyclohexylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be tricyclohexylphosphonium tetra-para-tolylborate. The analytical values and properties were as follows.

(1) Melting point: 129-131° C.

(2) IR spectrum (KBr) 2376 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.18-1.89 ppm (m, 30H, cyclohexyl secondary) 2.15 ppm (s, 12H, H₃C—C₆H₄—B) 2.51-2.57 ppm (m, 3H, cyclohexyl tertiary) 5.77 ppm (brd, 1H, J=470.4 Hz, H—P) 6.71 ppm (t, 8H, J=7.70 Hz, H₃C—C₆H₄—B) 7.03 ppm (brs, 8H, H₃C—C₆H₄—B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 20.8 ppm (s, H₃C—C₆H₄—B) 24.6 ppm (s, cyclohexyl secondary) 25.6 ppm (d, J=13.1 Hz, cyclohexyl secondary) 26.8 ppm (d, J=31.1 Hz, cyclohexyl tertiary) 27.0 ppm (s, cyclohexyl secondary) 125.9 ppm (dd, J=3.1 Hz, 5.6 Hz, H₃C—C₆H₄—B) 129.0 ppm (s, H₃C—C₆H₄quaternary-B) 135.5 ppm (d, J=1.2 Hz, H₃C—C₆H₄—B) 160.2 ppm (dd, J=49.4 Hz, 99.1 Hz, H₃C—C₆H₄quaternary-B)

Example B-17 Production of triisopropylphosphonium tetraphenylborate

The procedures in Example B-1 were repeated except that 6.4 g (40 mmol) of di-tert-butylmethylphosphine was replaced with 6.4 g (40 mmol) of triisopropylphosphine. Consequently, 16.9 g of objective triisopropylphosphonium tetraphenylborate was obtained as white crystal. The yield (mol %) was 88% based on triisopropylphosphine.

The crystal was analyzed by the methods indicated below and was identified to be triisopropylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 194-214° C. (decomposition temperature)

(2) IR spectrum (KBr) 2390 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.31 ppm (dt, 18H, J=17.4 Hz, 7.33 Hz, (H₃C)₂—CH—P) 2.82 ppm (dhep, 3H, J=12.3 Hz, 7.24 Hz, (H₃C)₂—CH—P) 5.93 ppm (brd, 1H, J=482.3 Hz, H—P) 6.79 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.93 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.19 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 17.2 ppm (d, J=2.5 Hz, (H₃C)₂—HC—P) 18.1 ppm (d, J=39.8 Hz, (H₃C)₂—HC—P) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=2.3 Hz, 5.2 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.1 Hz, 98.8 Hz, Ph quaternary-B)

Example B-18 Synthesis of 1-phenylheptane from n-heptyl bromide and phenylboronic acid Synthesis in which di-tert-butylmethylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.896 g (5 mmol) of n-heptyl bromide, 0.914 g (7.5 mmol) of phenylboronic acid, 0.056 g (0.25 mmol) of palladium (II) acetate, 1.683 g (15 mmol) of potassium tert-butoxide and 25 ml of tert-amyl alcohol were weighed in the flask, followed by stirring. Further, 0.240 g (0.5 mmol) of di-tert-butylmethylphosphonium tetraphenylborate obtained in Example B-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 24 hours. After the completion of the reaction, 20 ml of saturated sodium chloride solution was added, followed by separation. The organic phase was purified by column chromatography to afford 0.785 g of 1-phenylheptane (yield: 89 mol % based on n-heptyl bromide). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Example B-19 Synthesis of 4-n-heptyltoluene from n-heptyl bromide and para-tolylboronic acid Synthesis in which di-tert-butylmethylphosphonium tetraphenylborate was handled in air

The procedures in Example B-18 were repeated except that 0.914 g (7.5 mmol) of phenylboronic acid was replaced with 1.020 g (7.5 mmol) of para-tolylboronic acid. The organic phase was purified by column chromatography to afford 0.723 g of 4-n-heptyltoluene (yield: 76 mol % based on n-heptyl bromide) The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 190 (M⁺)

Example B-20 Synthesis of 1-phenylheptane from n-heptyl bromide and phenylboronic acid Synthesis in which di-tert-butylmethylphosphonium tetra-para-tolylborate was handled in air

The procedures in Example B-18 were repeated except that 0.240 g (0.5 mmol) of di-tert-butylmethylphosphonium tetraphenylborate was replaced with 0.268 g (0.5 mmol) of di-tert-butylmethylphosphonium tetra-para-tolylborate obtained in Example B-2. Consequently, 0.732 g of 1-phenylheptane was obtained (yield: 83 mol % based on n-heptyl bromide). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Example B-21 Similar to Example A-5 Synthesis of 2-ortho-tolylpyridine from 2-chloropyridine and ortho-tolylboronic acid Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.568 g (5 mmol) of 2-chloropyridine, 0.748 g (5.5 mmol) of ortho-tolylboronic acid, 0.011 g (0.05 mmol) of palladium (II) acetate, 0.959 g (17 mmol) of potassium fluoride and 10 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 24 hours. After the completion of the reaction, 10 ml of 10% aqueous sodium hydroxide solution was added, followed by separation. The organic phase was purified by column chromatography to afford 0.677 g of 2-ortho-tolylpyridine (yield: 80 mol % based on 2-chloropyridine). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 169 (M⁺)

Example B-22 Synthesis of 1-phenylheptane from n-heptyl bromide and phenylmagnesium chloride Synthesis in which di-tert-butylmethylphosphonium tetraphenylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 0.045 g (0.2 mmol) of palladium (II) acetate and 2 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.096 g (0.2 mmol) of di-tert-butylmethylphosphonium tetraphenylborate obtained in Example B-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 22° C. for 30 minutes. 3.582 g (20 mmol) of n-heptyl bromide was added, followed by stirring at 22° C. for 30 minutes. 10 ml (22 mmol) of 2.2M tetrahydrofuran solution of phenylmagnesium chloride was added dropwise at 30° C. over a period of 10 minutes, followed by stirring at 30° C. for 3 hours. After the completion of the reaction, 10 ml of saturated aqueous ammonium chloride solution was added, followed by separation. The organic phase was purified by column chromatography to afford 2.997 g of 1-phenylheptane (yield: 85 mol % based on n-heptyl bromide). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Example B-23 Similar to Example A-6 Synthesis of 4-methylbiphenyl from 4-bromotoluene and phenylmagnesium chloride Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 0.014 g (0.08 mmol) of palladium (II) chloride, 0.0194 g (0.19 mmol) of triethylamine and 5.5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.093 g (0.16 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 21° C. for 30 minutes. 1.368 g (8 mmol) of 4-bromotoluene was added, followed by stirring at 21° C. for 30 minutes. 4 ml (8.8 mmol) of 2.2M tetrahydrofuran solution of phenylmagnesium chloride was added dropwise at 21° C. over a period of 10 minutes, followed by stirring at 21° C. for 2 hours. After the completion of the reaction, 5 ml of saturated aqueous ammonium chloride solution was added, followed by separation. The organic phase was purified by column chromatography to afford 1.171 g of 4-methylbiphenyl (yield: 87 mol % based on 4-bromotoluene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 168 (M⁺)

Example B-24 Similar to Example A-7 Synthesis of 4-vinylbiphenyl from bromobenzene and 4-vinylphenylmagnesium chloride Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 0.0674 g (0.3 mmol) of palladium (II) acetate and 6 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.347 g (0.6 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 19° C. for 30 minutes. 4.710 g (30 mmol) of bromobenzene was added, followed by stirring at 19° C. for 30 minutes. 40 ml (50 mmol) of 1.25M tetrahydrofuran solution of 4-vinylphenylmagnesium chloride was added dropwise at 19° C. over a period of 2 hours, followed by stirring at 30° C. for 2 hours. After the completion of the reaction, 10 ml of saturated aqueous ammonium chloride solution was added, followed by separation. The organic phase was purified by column chromatography to afford 4.434 g of 4-vinylbiphenyl (yield: 82 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 180 (M⁺)

Example B-25 Similar to Example A-8 Synthesis of 1-phenylheptane from n-heptyl chloride and phenylmagnesium chloride Synthesis in which tricyclohexylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 0.027 g (0.12 mmol) of palladium (II) acetate and 7 ml of N-methylpyrrolidinone were weighed in the flask, followed by stirring. Further, 0.079 g (0.12 mmol) of tricyclohexylphosphonium tetra-para-tolylborate obtained in Example B-16 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.404 g (3 mmol) of n-heptyl chloride was added, followed by stirring at 25° C. for 30 minutes. 2 ml (4.4 mmol) of 2.2M tetrahydrofuran solution of phenylmagnesium chloride was added dropwise at 25° C. over a period of 10 minutes, followed by stirring at 25° C. for 19 hours. After the completion of the reaction, 6 ml of tetrahydrofuran and 10 ml of saturated aqueous ammonium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.434 g of 1-phenylheptane (yield: 82 mol % based on n-heptyl chloride). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Example B-26 Similar to Example A-9 Synthesis of 4-cyanobiphenyl from 4-chlorobenzonitrile and phenylzinc chloride Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate and 7 ml of N-methylpyrrolidinone were weighed in the flask, followed by stirring. Further, 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes to prepare a reaction liquid.

A 50-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 1.090 g (8 mmol) of zinc chloride and 4 ml of N-methylpyrrolidinone were weighed in the flask. The flask was purged with argon, followed by stirring. 3.4 ml (7.5 mmol) of 2.2M tetrahydrofuran solution of phenylmagnesium chloride was added dropwise at 25° C. over a period of 30 minutes, followed by stirring at 25° C. for 30 minutes. The reaction liquid previously obtained was added, followed by stirring at 25° C. for 30 minutes. Further, 0.688 g (5 mmol) of 4-chlorobenzonitrile was added, followed by stirring at 120° C. for 9 hours. After the completion of the reaction, 10 ml of toluene and 10 ml of saturated aqueous ammonium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.672 g of 4-cyanobiphenyl (yield: 75 mol % based on 4-chlorobenzonitrile). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 179 (M⁺)

Example B-27 Similar to Example A-10 Synthesis of 1-phenylheptane from chlorobenzene and n-heptylzinc chloride Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate and 7 ml of N-methylpyrrolidinone were weighed in the flask, followed by stirring. Further, 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes to prepare a reaction liquid.

A 50-ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 1.090 g (8 mmol) of zinc chloride and 4 ml of N-methylpyrrolidinone were weighed in the flask. The flask was purged with argon, followed by stirring. 3.5 ml (7 mmol) of 2M tetrahydrofuran solution of n-heptylmagnesium chloride was added dropwise at 25° C. over a period of 30 minutes, followed by stirring at 25° C. for 30 minutes. The reaction liquid previously obtained was added, followed by stirring at 25° C. for 30 minutes. Further, 0.558 g (5 mmol) of chlorobenzene was added, followed by stirring at 120° C. for 16 hours. After the completion of the reaction, 10 ml of toluene and 10 ml of saturated aqueous ammonium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.688 g of 1-phenylheptane (yield: 78 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Example B-28 Synthesis of 1-phenylheptane from n-heptyl bromide and trimethoxyphenylsilane Synthesis in which di-tert-butylmethylphosphonium tetraphenylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.358 g (2 mmol) of n-heptyl bromide, 0.476 g (2.4 mmol) of trimethoxyphenylsilane, 0.021 g (0.08 mmol) of palladium (II) bromide, 4.8 ml (4.8 mmol) of 1M tetrahydrofuran solution of tetra-n-butylammonium fluoride and 4.8 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.096 g (0.2 mmol) of di-tert-butylmethylphosphonium tetraphenylborate obtained in Example B-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 21 hours. After the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.300 g of 1-phenylheptane (yield: 85 mol % based on n-heptyl bromide). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Example B-29 Similar to Example A-11 Synthesis of 2-methylbiphenyl from 2-chlorotoluene and tri-n-butylphenyltin Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.045 g (0.2 mmol) of palladium (II) acetate, 1.337 g (8.8 mmol) of cesium fluoride and 4 ml of 1,4-dioxane were weighed in the flask, followed by stirring. Further, 0.463 g (0.8 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.506 g (4 mmol) of 2-chlorotoluene and 1.391 g (4.2 mmol) of tri-n-butylphenyltin were added, followed by stirring at 95° C. for 18 hours. After the completion of the reaction, 10 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.511 g of 2-methylbiphenyl (yield: 76 mol % based on 2-chlorotoluene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 168 (M⁺)

Example B-30 Similar to Example A-12 Synthesis of 2-methylbiphenyl from 2-bromotoluene and tri-n-butylphenyltin Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.045 g (0.2 mmol) of palladium (II) acetate, 1.337 g (8.8 mmol) of cesium fluoride and 4 ml of N-methylpyrrolidinone were weighed in the flask, followed by stirring. Further, 0.463 g (0.8 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.684 g (4 mmol) of 2-bromotoluene and 1.391 g (4.2 mmol) of tri-n-butylphenyltin were added, followed by stirring at 40° C. for 17 hours. After the completion of the reaction, 10 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.498 g of 2-methylbiphenyl (yield: 74 mol % based on 2-bromotoluene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 168 (M⁺)

Example B-31 Similar to Example A-13 Synthesis of (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester from 4-dimethylaminobromobenzene and methyl methacrylate Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 1.000 g (5 mmol) of 4-dimethylaminobromobenzene, 1.001 g (10 mmol) of methyl methacrylate, 0.011 g (0.012 mmol) of tris(dibenzylideneacetone)dipalladium (0), 1.074 g (5.5 mmol) of dicyclohexylmethylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 25 hours. After the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.954 g of (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester (yield: 87 mol % based on 4-dimethylaminobromobenzene). The identification of the product was made by H-NMR and ³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 2.15 ppm (s, 3H, H₃C—C) 2.98 ppm (s, 6H, H₃CN) 3.78 ppm (s, 3H, H₃CO) 6.69 ppm (d, J=8.8 Hz, 2H, ring proton) 7.37 ppm (d, J=8.8 Hz, 2H, ring proton) 7.62 ppm (s, 1H, HC═)

(2) ¹³C-NMR spectrum (δ in CDCl₃) 14.2, 40.1, 51.8, 111.6, 123.1, 123.7, 131.6, 139.4, 150.3, 169.8 ppm

Example B-32 Similar to Example A-14 Synthesis of (trans)-4-acetylstilbene from 4′-chloroacetophenone and styrene Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.773 g (5 mmol) of 4′-chloroacetophenone, 1.042 g (10 mmol) of styrene, 0.034 g (0.038 mmol) of tris(dibenzylideneacetone)dipalladium (0), 1.074 g (5.5 mmol) of dicyclohexylmethylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.087 g (0.15 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 37 hours. After the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.841 g of (trans)-4-acetylstilbene (yield: 75 mol % based on 4′-chloroacetophenone). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 222 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 2.60 ppm (s, 3H, H₃C) 7.11 ppm (d, J=16.5 Hz, 1H, HC═) 7.22 ppm (d, J=16.5 Hz, 1H, HC═) 7.24-40 ppm (m, 3H, ring proton) 7.53 ppm (d, J=7.2 Hz, 2H, ring proton) 7.57 ppm (d, J=8.7 Hz, 2H, ring proton) 7.94 ppm (d, J=8.7 Hz, 2H, ring proton)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 26.9, 126.6, 126.9, 127.5, 128.4, 128.9, 129.0, 131.5, 136.0, 136.8, 142.1, 197.5 ppm

Example B-33 Similar to Example A-15 Synthesis of (E)-3-(2,6-dimethylphenyl)-2-methylacrylic acid methyl ester from 2-chloro-meta-xylene and methyl methacrylate Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.703 g (5 mmol) of 2-chloro-meta-xylene, 1.001 g (10 mmol) of methyl methacrylate, 0.034 g (0.038 mmol) of tris(dibenzylideneacetone)dipalladium (0), 1.074 g (5.5 mmol) of dicyclohexylmethylamine and 5 ml of 1,4-dioxane were weighed in the flask, followed by stirring. Further, 0.087 g (0.15 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 120° C. for 37 hours. After the completion of the reaction, 5 ml of toluene and 10 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.775 g of (E)-3-(2,6-dimethylphenyl)-2-methylacrylic acid methyl ester (yield: 76 mol % based on 2-chloro-meta-xylene). The identification of the product was made by ¹H-NMR and 1³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 1.71 ppm (d, J=1.1 Hz, 3H, H₃C—C═) 2.18 ppm (s, 6H, H₃C) 3.84?ppm (s, 3H, H₃CO) 7.00-7.15 ppm (m, 3H, ring proton) 7.66 ppm (s, 1H, HC═)

(2) ¹³C-NMR spectrum (δ in CDCl₃) 13.6, 19.9, 51.8, 127.2, 127.3, 130.3, 135.0, 135.2, 139.0, 168.2 ppm

Example B-34 Similar to Example A-16 Synthesis of diphenylacetylene from bromobenzene and phenylacetylene Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 0.019 g (0.1 mmol) of copper (I) iodide, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.785 g (5 mmol) of bromobenzene and 1.021 g (10 mmol) of phenylacetylene were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.882 g of diphenylacetylene (yield: 99 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 178 (M⁺)

Example B-35 Similar to Example A-17 Synthesis of diphenylacetylene from bromobenzene and phenylacetylene Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.785 g (5 mmol) of bromobenzene and 0.613 g (6 mmol) of phenylacetylene were added, followed by stirring at 30° C. for 14 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.838 g of diphenylacetylene (yield: 94 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 178 (M⁺)

Example B-36 Similar to Example A-18 Synthesis of 4-[(trimethylsilyl)ethynyl]benzaldehyde from 4-bromobenzaldehyde and trimethylsilylacetylene Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, 20 a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 0.019 g (0.1 mmol) of copper (I) iodide, 1.088 g (6 mmol) of dicyclohexylamine and 9 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.925 g (5 mmol) of 4-bromobenzaldehyde and 0.589 g (6 mmol) of trimethylsilylacetylene were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.890 g of 4-[(trimethylsilyl)ethynyl]benzaldehyde (yield: 88 mol % based on 4-bromobenzaldehyde). The identification of the product was made by ¹H-NMR and ¹³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 0.26 ppm (s, 9H, H₃C) 7.59 ppm (d, J=8.1 Hz, 2H, ring proton) 7.81 ppm (d, J=8.1 Hz, 2H, ring proton) 9.99 ppm (s, 1H, HC)

(2) ¹³C-NMR spectrum (δ in CDCl₃) −0.2, 99.0, 103.8, 129.3, 129.4, 132.5, 135.6, 191.4 ppm

Example B-37 Similar to Example A-19 Synthesis of 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol from 4-bromo-N,N-dimethylaniline and 2-methyl-3-butyne-2-ol Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 0.019 g (0.1 mmol) of copper (I) iodide, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 1.000 g (5 mmol) of 4-bromo-N,N-dimethylaniline and 0.505 g (6 mmol) of 2-methyl-3-butyne-2-ol were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.875 g of 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol (yield: 86 mol % based on 4-bromo-N,N-dimethylaniline). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 203 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 1.58 ppm (s, 6H, H₃CC) 2.86 ppm (s, 6H, H₃CN) 3.38 ppm (s, 1H, HO) 6.54 ppm .(d, J=9.0 Hz, 2H, ring proton) 7.76 ppm (d, J=9.0 Hz, 2H, ring proton)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 31.4, 39.8, 65.0, 82.4, 91.6, 109.6, 111.6, 132.3, 149.7 ppm

Example B-38 Similar to Example A-20 Synthesis of (4-fluorophenyl)-2-methyl-3-butyne-2-ol from 1-bromo-4-fluorobenzene and 2-methyl-3-butyne-2-ol Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.875 g (5 mmol) of 1-bromo-4-fluorobenzene and 0.505 g (6 mmol) of 2-methyl-3-butyne-2-ol were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.862 g of (4-fluorophenyl)-2-methyl-3-butyne-2-ol (yield: 97 mol % based on 1-bromo-4-fluorobenzene). The identification of the product was made by ¹H-NMR and ¹³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 1.59 ppm (s, 6H, H₃C) 3.41 ppm (s, 1H, HO) 6.88-6.95 ppm (m, 2H, ring proton) 7.30-7.36 ppm (m, 2H, ring proton)

(2) ¹³C-NMR spectrum (δ in CDCl₃) 31.5, 65.3, 80.8, 93.6, 115.3 (d, J=21.8 Hz), 122.1 (d, J=492.3 Hz), 133.3 (d, J=8.7 Hz), 162.2 (d, J=249.2 Hz) ppm

Example B-39 Similar to Example A-21 Synthesis of 1,2-diphenyl-1-propanone from chlorobenzene and propiophenone Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate, 0.721 g (7.5 mmol) of sodium-tert-butoxide and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.058 g (0.1 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 22° C. for 30 minutes. 0.563 g (5 mmol) of chlorobenzene was added, followed by stirring at 22° C. for 30 minutes. 0.738 g (5.5 mmol) of propiophenone was added, followed by stirring at 70° C. for 6 hours. After the completion of the reaction, 2.5 ml of water was added, followed by separation. The organic phase was purified by column chromatography to afford 0.810 g of 1,2-diphenyl-1-propanone (yield: 77 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 210 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 1.54 ppm (d, J=6.8 Hz, 3H, H₃C) 4.70 ppm (q, J=6.8 Hz, 1H, HC) 7.17-7.23 ppm (m, 1H, Ph) 7.29-7.30 ppm (m, 4H, Ph) 7.37-7.40 ppm (m, 2H, Ph) 7.48 ppm (t, J=7.3 Hz, 1H, Ph) 7.95 ppm (d, J=7.3 Hz, 2H, Ph)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 19.6, 47.9, 127.0, 127.8, 128.5, 128.8, 129.0, 132.3, 136.5, 141.6, 200.3 ppm

Example B-40 Similar to Example A-22 Synthesis of 1,2-diphenyl-1-propanone from bromobenzene and propiophenone Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.011 g (0.05 mmol) of palladium (II) acetate, 1.442 g (15 mmol) of sodium-tert-butoxide and 10 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 1.570 g (10 mmol) of bromobenzene was added, followed by stirring at 25° C. for 30 minutes. 1.476 g (11 mmol) of propiophenone was added, followed by stirring at 25° C. for 17 hours. After the completion of the reaction, 5 ml of water was added, followed by separation. The organic phase was purified by column chromatography to afford 2.061 g of 1,2-diphenyl-1-propanone (yield: 98 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 210 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 1.54 ppm (d, J=6.8 Hz, 3H, H₃C) 4.70 ppm (q, J=6.8 Hz, 1H, HC) 7.17-7.23 ppm (m, 1H, Ph) 7.29-7.30 ppm (m, 4H, Ph) 7.37-7.40 ppm (m, 2H, Ph) 7.48 ppm (t, J=7.3 Hz, 1H, Ph) 7.95 ppm (d, J=7.3 Hz, 2H, Ph)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 19.6, 47.9, 127.0, 127.8, 128.5, 128.8, 129.0, 132.3, 136.5, 141.6, 200.3 ppm

Example B-41 Similar to Example A-23 Synthesis of di-tert-butylphenyl malonate from chlorobenzene and di-tert-butyl malonate Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.013 g (0.06 mmol) of palladium (II) acetate, 0.317 g (3.3 mmol) of sodium-tert-butoxide and 9 ml of dioxane were weighed in the flask, followed by stirring. Further, 0.035 g (0.06 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.338 g (3 mmol) of chlorobenzene was added, followed by stirring at 25° C. for 30 minutes. 0.714 g (3.3 mmol) of di-tert-butyl malonate was added, followed by stirring at 100° C. for 12 hours. After the completion of the reaction, 9 ml of tetrahydrofuran and 9 ml of water were added, followed by separation. The organic phase was purified by column chromatography to afford 0.744 g of di-tert-butylphenyl malonate (yield: 85 mol % based on chlorobenzene). The identification of the product was made by ¹H-NMR and ¹³C-NMR.

(1) ¹H-NMR spectrum (δ in CDCl₃) 1.47 ppm (s, 18H, H₃C) 4.44 ppm (s, 1H, HC) 7.33-7.40 ppm (m, 5H, Ph)

(2) ¹³C-NMR spectrum (δ in CDCl₃) 27.9, 60.1, 81.9, 127.8, 128.4, 129.3, 133.5, 167.4 ppm

Example B-42 Similar to Example A-24 Synthesis of ethyl-2-phenylcyanoacetate from chlorobenzene and ethyl cyanoacetate Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate, 2.459 g (15 mmol) of sodium phosphate and 15 ml of toluene were weighed in the flask, followed by stirring. Further, 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.563 g (5 mmol) of chlorobenzene was added, followed by stirring at 25° C. for 30 minutes. 0.622 g (5.5 mmol) of ethyl cyanoacetate was added, followed by stirring at 100° C. for 12 hours. After the completion of the reaction, 5 ml of water was added, followed by separation. The organic phase was purified by column chromatography to afford 0.502 g of ethyl-2-phenylcyanoacetate (yield: 53 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 189 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 1.29 ppm (t, J=7.2 Hz, 3H, H₃C) 4.21-4.29 ppm (m, 2H, H₂C) 4.73 ppm (s, 1H, HC) 7.42-7.49 ppm (m, 5H, Ph)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 13.9, 43.7, 63.3, 115.7, 127.9, 129.2, 129.3, 130.0, 165.0 ppm

Example B-43 Similar to Example A-25 Synthesis of triphenylamine from chlorobenzene and diphenylamine Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 5.403 g (48 mmol) of chlorobenzene, 6.769 g (40 mmol) of diphenylamine, 4.613 g (48 mmol) of sodium-tert-butoxide, 0.002 g (0.01 mmol) of palladium (II) acetate and 5 ml of xylene were weighed in the flask, followed by stirring. Further, 0.023 g (0.04 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 100-120° C. for 10 hours. After the completion of the reaction, 45 ml of xylene and 50 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 9.028 g of triphenylamine (yield: 92 mol % based on diphenylamine). The melting point was 125-126° C.

Example B-44 Similar to Example A-26 Synthesis of tert-butyl-2-methylphenyl ether from 2-chlorotoluene and sodium-tert-butoxide Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 6.330 g (50 mmol) of 2-chlorotoluene, 5.766 g (60 mmol) of sodium-tert-butoxide, 0.112 g (0.5 mmol) of palladium (II) acetate and 50 ml of xylene were weighed in the flask, followed by stirring. Further, 0.868 g (1.5 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 125° C. for 3 hours. After the completion of the reaction, 10 ml of water was added, followed by separation. The organic phase was purified by distillation to afford 7.720 g of tert-butyl-2-methylphenyl ether (yield: 94 mol % based on 2-chlorotoluene). The boiling point was 75° C./9 Torr.

Example B-45 Similar to Example A-27 Synthesis of 2-methoxy-4,2′-dimethylphenyl ether from 2-chlorotoluene and 2-methoxy-4-methylphenol Synthesis in which tri-tert-butylphosphonium tetra-para-tolylborate was handled in air

A 200-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 1.920 g (48 mmol) of 60 wt % sodium hydride and 50 ml of toluene were weighed in the flask. The flask was purged with argon, followed by stirring. 6.632 g (48 mmol) of 2-methoxy-4-methylphenol was added, followed by stirring at 25° C. for 30 minutes. Further, 5.064 g (40 mmol) of 2-chlorotoluene and 0.449 g (2 mmol) of palladium (II) acetate were added, followed by stirring. Further, 1.157 g (2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask, followed by stirring at 104° C. for 9 hours. After the completion of the reaction, 50 ml of saturated sodium chloride solution was added, followed by separation. The organic phase was purified by column chromatography to afford 6.849 g of 2-methoxy-4,2′-dimethylphenyl ether (yield: 75 mol % based on 2-chlorotoluene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR.

(1) Mass spectrum [EI mode] M/Z 228 (M⁺)

(2) ¹H-NMR spectrum (δ in CDCl₃) 2.32 ppm (s, 3H, H₃C) 2.34 ppm (s, 3H, H₃C) 3.84 ppm (s, 3H, H₃CO) 6.68-6.81 ppm (m, 4H, ring proton) 6.95-7.22 ppm (m, 3H, ring proton)

(3) ¹³C-NMR spectrum (δ in CDCl₃) 16.2, 21.2, 56.0, 113.7, 117.1, 117.2, 119.3, 121.3, 122.8, 126.8, 131.1, 133.7, 143.8, 150.5, 155.8 ppm

Example B-46 Production of tricyclopentylphosphonium tetraphenylborate

A 200-ml four-necked flask sufficiently purged with nitrogen was equipped with a stirrer, a thermometer and a reflux condenser. 5.5 g (40 mmol) of trichlorophosphine and 40.0 ml of tetrahydrofuran were weighed in the flask. A cyclopentylmagnesium chloride solution was added dropwise to the flask at an internal temperature of 10-20° C. over a period of 3 hours, wherein the solution had been previously prepared from 13.8 g (132 mmol) of cyclopentyl chloride and 3.2 g (132 mmol) of metallic magnesium in 49 g of tetrahydrofuran. The mixture was stirred at 20-30° C. for 2 hours. Gas chromatography analysis confirmed the disappearance of trichlorophosphine. After the completion of the reaction, 61 ml of toluene was added, and 11.8 g (6 mmol) of 5% sulfuric acid was added dropwise to dissolve the magnesium salt, followed by separation. The organic phase was washed with 11.8 ml of water, and a solution of tricyclopentylphosphine was obtained.

A 100-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. The solution of tricyclopentylphosphine prepared above was weighed in the flask, to which 8.0 ml (40 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of tricyclopentylphosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 8.0 ml of heptane. The aqueous phase was assumed to contain tricyclopentylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 15.1 g (44 mmol) of sodium tetraphenylborate and 60 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of tricyclopentylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 16.8 g of objective tricyclopentylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 75% based on trichlorophosphine.

The crystal was analyzed by the methods indicated below and was identified to be tricyclopentylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 178-187° C. (decomposition)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 1.18-1.77 ppm (m, 24H, cyclopentyl secondary) 2.43-2.56 ppm (m, 3H, cyclopentyl tertiary) 5.76 ppm (brd, 1H, J=470.6 Hz, H—P) 6.79 ppm (t, 4H, J=7.34 Hz, Ph-B) 6.93 ppm (t, 8H, J=7.34 Hz, Ph-B) 7.19 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 25.6 ppm (d, J=13.1 Hz, cyclopentyl secondary) 26.8 ppm (d, J=39.8 Hz, cyclopentyl tertiary) 27.0 ppm (d, J=3.1 Hz, cyclopentyl secondary) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=3.1 Hz, 5.6 Hz, Ph-B) 135.5 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.1 Hz, 98.8 Hz, Ph quaternary-B)

Example B-47 Production of n-butyldicyclohexylphosphonium tetraphenylborate

A 100-ml four-necked flask sufficiently purged with nitrogen was equipped with a stirrer, a thermometer and a reflux condenser. 9.3 g (40 mmol) of dicyclohexylphosphinas chloride and 7.2 ml of tetrahydrofuran were weighed in the flask. A n-butylmagnesium chloride solution was added dropwise to the flask at an internal temperature of 10-20° C. over a period of 1 hour, wherein the solution had been previously prepared from 4.8 g (52 mmol) of n-butyl chloride and 1.3 g (52 mmol) of metallic magnesium in 20 g of tetrahydrofuran. The mixture was stirred at 20-30° C. for 2 hours. Gas chromatography analysis confirmed the disappearance of dicyclohexylphosphinas chloride. After the completion of the reaction, 26 ml of toluene was added, and 11.8 g (6 mmol) of 5% sulfuric acid was added dropwise to dissolve the magnesium salt, followed by separation. The organic phase was washed with 11.8 ml of water, and a solution of n-butyldicyclohexylphosphine was obtained.

A 100-ml four-necked flask sufficiently purged with argon was equipped with a stirrer, a thermometer and a reflux condenser. The solution of n-butyldicyclohexylphosphine prepared above was weighed in the flask, to which 8.0 ml (40 mmol) of 5N hydrochloric acid was added, followed by stirring at 25° C. for 1 hour. The organic phase was analyzed by gas chromatography, which confirmed the disappearance of n-butyldicyclohexylphosphine. After the completion of the reaction, the liquid was separated and the aqueous phase was washed with 8.0 ml of heptane. The aqueous phase was assumed to contain n-butyldicyclohexylphosphine hydrochloride dissolved therein.

A 300-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 15.1 g (44 mmol) of sodium tetraphenylborate and 60 ml of water were weighed in the flask, followed by stirring to dissolve sodium tetraphenylborate. While the stirring was continuously carried out, the aqueous solution of n-butyldicyclohexylphosphine hydrochloride previously obtained was added to the solution, and the mixture was stirred at 25° C. for 3 hours. After the completion of the reaction, the precipitated product was filtered off. The so obtained crystal was suspended in 100 ml of toluene at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of toluene. The crystal was then suspended in 100 ml of methanol at 50° C., and the suspension was cooled to 25° C. and filtered. The product filtered off was washed with 100 ml of methanol. The crystal obtained was dried to give 17.2 g of objective n-butyldicyclohexylphosphonium tetraphenylborate as white crystal. The yield (mol %) was 75% based on dicyclohexylphosphinas chloride.

The crystal was analyzed by the methods indicated below and was identified to be n-butyldicyclohexylphosphonium tetraphenylborate. The analytical values and properties were as follows.

(1) Melting point: 175-180° C. (decomposition temperature)

(2) IR spectrum (KBr) 2359 cm⁻¹

(3) ¹H-NMR spectrum (δ in DMSO-d6) 0.93 ppm (t, 3H, J=7.34 Hz, H₃C—(CH₂)₃—P) 1.17-1.89 ppm (m, 24H, cyclohexyl secondary, H₃C—(CH₂)₃—P) 2.28-2.56 ppm (m, 4H, cyclohexyl tertiary, H₃C—(CH₂)₃—P) 5.34-7.18 ppm (brd, 1H, H—P) 6.79 ppm (t, 4H, J=7.15 Hz, Ph-B) 6.92 ppm (t, 8H, J=7.15 Hz, Ph-B) 7.19 ppm (brs, 8H, Ph-B)

(4) ¹³C-NMR spectrum (δ in DMSO-d6) 13.1 ppm (s, CH₃—CH₂—CH₂—CH₂—P) 14.3 ppm (d, J=43.2 Hz, CH₃—CH₂—CH₂—cH₂—P) 23.0 ppm (d, J=14.3 Hz, CH₃—CH₂—CH₂—CH₂—P) 24.6 ppm (d, J=1.2 Hz, cyclohexyl secondary) 25.9 ppm (d, J=12.5 Hz, cyclohexyl secondary) 26.2 ppm (d, J=5.0 Hz, CH₃—CH₂—CH₂—CH₂—P) 27.9 ppm (d, J=3.4 Hz, cyclohexyl secondary) 28.8 ppm (d, J=37.0 Hz, cyclohexyl tertiary) 121.4 ppm (s, Ph-B) 125.2 ppm (dd, J=3.1 Hz, 5.6 Hz, Ph-B) 135.6 ppm (d, J=1.2 Hz, Ph-B) 163.3 ppm (dd, J=49.1 Hz, 98.8 Hz, Ph quaternary-B)

Example B-48 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which n-butyldicyclohexylphosphonium tetraphenylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 7.536 g (48 mmol) of bromobenzene, 6.769 g (40 mmol) of diphenylamine, 4.613 g (48 mmol) of sodium-tert-butoxide, 0.090 g (0.40 mmol) of palladium (II) acetate and 5 ml of xylene were weighed in the flask, followed by stirring. Further, 0.690 g (1.20 mmol) of n-butyldicyclohexylphosphonium tetraphenylborate obtained in Example B-47 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 125° C. for 4 hours. After the completion of the reaction, 45 ml of xylene and 50 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 8.345 g of triphenylamine (yield: 85 mol % based on diphenylamine). The melting point was 125-126° C.

Example B-49 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which di-tert-butylphenylphosphonium tetraphenylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 7.536 g (48 mmol) of bromobenzene, 6.769 g (40 mmol) of diphenylamine, 4.613 g (48 mmol) of sodium-tert-butoxide, 0.009 g (0.04 mmol) of palladium (II) acetate and 5 ml of xylene were weighed in the flask, followed by stirring. Further, 0.065 g (0.12 mmol) of di-tert-butylphenylphosphonium tetraphenylborate obtained in Example B-9 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 125° C. for 4 hours. After the completion of the reaction, 45 ml of xylene and 50 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 9.028 g of triphenylamine (yield: 92 mol % based on diphenylamine). The melting point was 125-126° C.

Example B-50 Synthesis of triphenylamine from bromobenzene and biphenylamine Synthesis in which 2-biphenylyl-di-tert-butylphosphonium tetraphenylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 7.536 g (48 mmol) of bromobenzene, 6.769 g (40 mmol) of diphenylamine, 4.613 g (48 mmol) of sodium-tert-butoxide, 0.009 g (0.04 mmol) of palladium (II) acetate and 5 ml of xylene were weighed in the flask, followed by stirring. Further, 0.074 g (0.12 mmol) of 2-biphenylyl-di-tert-butylphosphonium tetraphenylborate obtained in Example B-10 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 125° C. for 4 hours. After the completion of the reaction, 45 ml of xylene and 50 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 8.537 g of triphenylamine (yield: 87 mol % based on diphenylamine). The melting point was 125-126° C.

Example B-51 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which di-tert-butyl-1-naphthylphosphonium tetraphenylborate was handled in air

A 100-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 7.536 g (48 mmol) of bromobenzene, 6.769 g (40 mmol) of diphenylamine, 4.613 g (48 mmol) of sodium-tert-butoxide, 0.009 g (0.04 mmol) of palladium (II) acetate and 5 ml of xylene were weighed in the flask, followed by stirring. Further, 0.071 g (0.12 mmol) of di-tert-butyl-1-naphthylphosphonium tetraphenylborate obtained in Example B-11 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 125° C. for 4 hours. After the completion of the reaction, 45 ml of xylene and 50 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 8.341 g of triphenylamine (yield: 85 mol % based on diphenylamine). The melting point was 125-126° C.

Comparative Example 1 Synthesis of 1-phenylheptane from n-heptyl bromide and phenylboronic acid Synthesis in which di-tert-butylmethylphosphine was handled in argon

The procedures in Example B-18 were repeated except that 0.240 g (0.5 mmol) of di-tert-butylmethylphosphonium tetraphenylborate of Example B-18 was replaced with 0.080 g (0.5 mmol) of di-tert-butylmethylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.749 g of 1-phenylheptane was obtained (yield: 85 mol % based on n-heptyl bromide). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 176 (M⁺)

Comparative Example 2 Synthesis of 1-phenylheptane from n-heptyl bromide and phenylboronic acid Synthesis in which di-tert-butylmethylphosphine was handled in air

The procedures in Example B-18 were repeated except that 0.240 g (0.5 mmol) of di-tert-butylmethylphosphonium tetraphenylborate of Example B-18 was replaced with 0.080 g (0.5 mmol) of di-tert-butylmethylphosphine. Di-tert-butylmethylphosphine generated white smoke while being handled in air. Little 1-phenylheptane formed.

Comparative Example 3 Synthesis of 2-ortho-tolylpyridine from 2-chloropyridine and ortho-tolylboronic acid Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-S or B-21 were repeated except that 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-5 or 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-21 was replaced with 0.010 g (0.05 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.694 g of 2-ortho-tolylpyridine was obtained (yield: 82 mol % based on 2-chloropyridine). The identification of the product was made by mass spectroscopy.

Mass spectrum [EI mode] M/Z 169 (M⁺)

Comparative Example 4 Synthesis of 2-ortho-tolylpyridine from 2-chloropyridine and ortho-tolylboronic acid Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-S or B-21 were repeated except that 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-5 or 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-21 was replaced with 0.010 g (0.05 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 2-ortho-tolylpyridine formed.

Comparative Example 5 Synthesis of 1-phenylheptane from n-heptyl bromide and phenylmagnesium chloride Synthesis in which di-tert-butylmethylphosphine was handled in argon

The procedures in Example B-22 were repeated except that 0.096 g (0.2 mmol) of di-tert-butylmethylphosphonium tetraphenylborate of Example B-22 was replaced with 0.032 g (0.2 mmol) of di-tert-butylmethylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 2.992 g of 1-phenylheptane was obtained (yield: 85 mol % based on n-heptyl bromide). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example B-22.

Comparative Example 6 Synthesis of 1-phenylheptane from n-heptyl bromide and phenylmagnesium chloride Synthesis in which di-tert-butylmethylphosphine was handled in air

The procedures in Example B-22 were repeated except that 0.096 g (0.2 mmol) of di-tert-butylmethylphosphonium tetraphenylborate of Example B-22 was replaced with 0.032 g (0.2 mmol) of di-tert-butylmethylphosphine. Di-tert-butylmethylphosphine generated white smoke while being handled in air. Little 1-phenylheptane formed.

Comparative Example 7 Synthesis of 4-methylbiphenyl from 4-bromotoluene and phenylmagnesium chloride Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-6 or B-23 were repeated except that 0.084 g (0.16 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-6 or 0.093 g (0.16 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-23 was replaced with 0.032 g (0.16 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 1.184 g of 4-methylbiphenyl was obtained (yield: 88 mol % based on 4-bromotoluene). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-6 or B-23.

Comparative Example 8 Synthesis of 4-methylbiphenyl from 4-bromotoluene and phenylmagnesium chloride Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-6 or B-23 were repeated except that 0.084 g (0.16 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-6 or 0.093 g (0.16 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-23 was replaced with 0.032 g (0.16 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 4-methylbiphenyl formed.

Comparative Example 9 Synthesis of 4-vinylbiphenyl from bromobenzene and 4-vinylphenylmagnesium chloride Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-7 or B-24 were repeated except that 0.314 g (0.6 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-7 or 0.347 g (0.6 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-24 was replaced with 0.121 g (0.6 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 4.434 g of 4-vinylbiphenyl was obtained (yield: 82 mol % based on bromobenzene). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-7 or B-24.

Comparative Example 10 Synthesis of 4-vinylbiphenyl from bromobenzene and 4-vinylphenylmagnesium chloride Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-7 or B-24 were repeated except that 0.314 g (0.6 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-7 or 0.347 g (0.6 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-24 was replaced with 0.121 g (0.6 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 4-vinylbiphenyl formed.

Comparative Example 11 Synthesis of 1-phenylheptane from n-heptyl chloride and phenylmagnesium chloride Synthesis in which tricyclohexylphosphine was handled in argon

The procedures in Example A-8 or B-25 were repeated except that 0.072 g (0.12 mmol) of tricyclohexylphosphonium tetraphenylborate of Example A-8 or 0.079 g (0.12 mmol) of tricyclohexylphosphonium tetra-para-tolylborate of Example B-25 was replaced with 0.034 g (0.12 mmol) of tricyclohexylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.434 g of 1-phenylheptane was obtained (yield: 82 mol % based on n-heptyl chloride). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-8 or B-25.

Comparative Example 12 Synthesis of 1-phenylheptane from n-heptyl chloride and phenylmagnesium chloride Synthesis in which tricyclohexylphosphine was handled in air

The procedures in Example A-8 or B-25 were repeated except that 0.072 g (0.12 mmol) of tricyclohexylphosphonium tetraphenylborate of Example A-8 or 0.079 g (0.12 mmol) of tricyclohexylphosphonium tetra-para-tolylborate of Example B-25 was replaced with 0.034 g (0.12 mmol) of tricyclohexylphosphine. Tricyclohexylphosphine generated white smoke while being handled in air. Little 1-phenylheptane formed.

Comparative Example 13 Synthesis of 4-cyanobiphenyl from 4-chlorobenzonitrile and phenylzinc chloride Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-9 or B-26 were repeated except that 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-9 or 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-26 was replaced with 0.040 g (0.2 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.672 g of 4-cyanobiphenyl was obtained (yield: 75 mol % based on 4-chlorobenzonitrile). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-9 or B-26.

Comparative Example 14 Synthesis of 4-cyanobiphenyl from 4-chlorobenzonitrile and phenylzinc chloride Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-9 or B-26 were repeated except that 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-9 or 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-26 was replaced with 0.040 g (0.2 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 4-cyanobiphenyl formed.

Comparative Example 15 Synthesis of 1-phenylheptane from chlorobenzene and n-heptylzinc chloride Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-10 or B-27 were repeated except that 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-10 or 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-27 was replaced with 0.040 g (0.2 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.688 g of 1-phenylheptane was obtained (yield: 78 mol % based on chlorobenzene). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-10 or B-27.

Comparative Example 16 Synthesis of 1-phenylheptane from chlorobenzene and n-heptylzinc chloride Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-10 or B-27 were repeated except that 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-10 or 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-27 was replaced with 0.040 g (0.2 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 1-phenylheptane formed.

Comparative Example 17 Synthesis of 1-phenylheptane from n-heptyl bromine and trimethoxyphenylsilane Synthesis in which di-tert-butylmethylphosphine was handled in argon

The procedures in Example B-28 were repeated except that 0.096 g (0.2 mmol) of di-tert-butylmethylphosphonium tetraphenylborate of Example B-28 was replaced with 0.032 g (0.2 mmol) of di-tert-butylmethylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.300 g of 1-phenylheptane was obtained (yield: 85 mol % based on n-heptyl bromide). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example B-28.

Comparative Example 18 Synthesis of 1-phenylheptane from n-heptyl bromine and trimethoxyphenylsilane Synthesis in which di-tert-butylmethylphosphine was handled in air

The procedures in Example B-28 were repeated except that 0.096 g (0.2 mmol) of di-tert-butylmethylphosphonium tetraphenylborate of Example B-28 was replaced with 0.032 g (0.2 mmol) of di-tert-butylmethylphosphine. Di-tert-butylmethylphosphine generated white smoke while being handled in air. Little 1-phenylheptane formed.

Comparative Example 19 Synthesis of 2-methylbiphenyl from 2-chlorotoluene and tri-n-butylphenyltin Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-11 or B-29 were repeated except that 0.418 g (0.8 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-11 or 0.463 g (0.8 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-29 was replaced with 0.162 g (0.8 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.513 g of 2-methylbiphenyl was obtained (yield: 76 mol % based on 2-chlorotoluene). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-11 or B-29.

Comparative Example 20 Synthesis of 2-methylbiphenyl from 2-chlorotoluene and tri-n-butylphenyltin Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-11 or B-29 were repeated except that 0.418 g (0.8 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-11 or 0.463 g (0.8 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-29 was replaced with 0.162 g (0.8 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 2-methylbiphenyl formed.

Comparative Example 21 Synthesis of 2-methylbiphenyl from 2-bromotoluene and tri-n-butylphenyltin Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-12 or B-30 were repeated except that 0.418 g (0.8 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-12 or 0.463 g (0.8 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-30 was replaced with 0.162 g (0.8 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.472 g of 2-methylbiphenyl was obtained (yield: 70 mol % based on 2-bromotoluene). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-12 or B-30.

Comparative Example 22 Synthesis of 2-methylbiphenyl from 2-bromotoluene and tri-n-butylphenyltin Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-12 or B-30 were repeated except that 0.418 g (0.8 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-12 or 0.463 g (0.8 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-30 was replaced with 0.162 g (0.8 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 2-methylbiphenyl formed.

Comparative Example 23 Synthesis of (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester from 4-dimethylaminobromobenzene and methyl methacrylate Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-13 or B-31 were repeated except that 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-13 or 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-31 was replaced with 0.010 g (0.05 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.944 g of (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester was obtained (yield: 86 mol % based on 4-dimethylaminobromobenzene). The identification of the product was made by ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-13 or B-31.

Comparative Example 24 Synthesis of (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester from 4-dimethylaminobromobenzene and methyl methacrylate Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-13 or B-31 were repeated except that 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-13 or 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-31 was replaced with 0.010 g (0.05 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little (E)-3-(4-dimethylaminophenyl)-2-methylacrylic acid methyl ester formed.

Comparative Example 25 Synthesis of (trans)-4-acetylstilbene from 4′-chloroacetophenone and styrene Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-14 or B-32 were repeated except that 0.078 g (0.15 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-14 or 0.087 g (0.15 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-32 was replaced with 0.030 g (0.15 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.828 g of (trans)-4-acetylstilbene was obtained (yield: 75 mol % based on 4′-chloroacetophenone). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-14 or B-32.

Comparative Example 26 Synthesis of (trans)-4-acetylstilbene from 4′-chloroacetophenone and styrene Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-14 or B-32 were repeated except that 0.078 g (0.15 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-14 or 0.087 g (0.15 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-32 was replaced with 0.030 g (0.15 =mol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little (trans)-4-acetylstilbene formed.

Comparative Example 27 Synthesis of (E)-3-(2,6-dimethylphenyl)-2-methylacrylic acid methyl ester from 2-chloro-meta-xylene and methyl methacrylate Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-15 or B-33 were repeated except that 0.078 g (0.15 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-15 or 0.087 g (0.15 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-33 was replaced with 0.030 g (0.15 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.776 g of (E)-3-(2,6-dimethylphenyl)-2-methylacrylic acid methyl ester was obtained (yield: 76 mol % based on 2-chloro-meta-xylene) The identification of the product was made by H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-15 or B-33.

Comparative Example 28 Synthesis of (E)-3-(2,6-dimethylphenyl)-2-methylacrylic acid methyl ester from 2-chloro-meta-xylene and methyl methacrylate Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-15 or B-33 were repeated except that 0.078 g (0.15 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-15 or 0.087 g (0.15 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-33 was replaced with 0.030 g (0.15 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little (E)-3-(2,6-dimethylphenyl)-2-methylacrylic acid methyl ester formed.

Comparative Example 29 Synthesis of diphenylacetylene from bromobenzene and phenylacetylene Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-16 or B-34 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-16 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-34 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.869 g of diphenylacetylene was obtained (yield: 98 mol % based on bromobenzene). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-16 or B-34.

Comparative Example 30 Synthesis of diphenylacetylene from bromobenzene and phenylacetylene Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-16 or B-34 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-16 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-34 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little diphenylacetylene formed.

Comparative Example 31 Synthesis of diphenylacetylene from bromobenzene and phenylacetylene Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-17 or B-35 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-17 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-35 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.833 g of diphenylacetylene was obtained (yield: 94 mol % based on bromobenzene). The identification of the product was made on the basis of a mass spectrum, which was in agreement with that of Example A-17 or B-35.

Comparative Example 32 Synthesis of diphenylacetylene from bromobenzene and phenylacetylene Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-17 or B-35 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-17 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-35 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little diphenylacetylene formed.

Comparative Example 33 Synthesis of 4-[(trimethylsilyl)ethynyl]benzaldehyde from 4-bromobenzaldehyde and trimethylsilylacetylene Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-18 or B-36 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-18 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-36 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.894 g of 4-[(trimethylsilyl)ethynyl]benzaldehyde was obtained (yield: 88 mol % based on 4-bromobenzaldehyde). The identification of the product was made by ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-18 or B-36.

Comparative Example 34 Synthesis of 4-[(trimethylsilyl)ethynyl]benzaldehyde from 4-bromobenzaldehyde and trimethylsilylacetylene Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-18 or B-36 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-18 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-36 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 4-[(trimethylsilyl)ethynyl]benzaldehyde formed.

Comparative Example 35 Synthesis of 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol from 4-bromo-N,N-dimethylaniline and 2-methyl-3-butyne-2-ol Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-19 or B-37 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-19 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-37 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.874 g of 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol was obtained (yield: 86 mol % based on 4-bromo-N,N-dimethylaniline). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-19 or B-37.

Comparative Example 36 Synthesis of 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol from 4-bromo-N,N-dimethylaniline and 2-methyl-3-butyne-2-ol Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-19 or B-37 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-19 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-37 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol formed.

Comparative Example 37 Synthesis of (4-fluorophenyl)-2-methyl-3-butyne-2-ol from 1-bromo-4-fluorobenzene and 2-methyl-3-butyne-2-ol Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-20 or B-38 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-20 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-38 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.860 g of (4-fluorophenyl)-2-methyl-3-butyne-2-ol was obtained (yield: 97 mol % based on 1-bromo-4-fluorobenzene). The identification of the product was made by ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-20 or B-38.

Comparative Example 38 Synthesis of (4-fluorophenyl)-2-methyl-3-butyne-2-ol from 1-bromo-4-fluorobenzene and 2-methyl-3-butyne-2-ol Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-20 or B-38 were repeated except that 0.157 g (0.3 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-20 or 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-38 was replaced with 0.061 g (0.3 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little (4-fluorophenyl)-2-methyl-3-butyne-2-ol formed.

Comparative Example 39 Synthesis of 1,2-diphenyl-1-propanone from chlorobenzene and propiophenone Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-21 or B-39 were repeated except that 0.052 g (0.1 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-21 or 0.058 g (0.1 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-39 was replaced with 0.020 g (0.1 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.789 g of 1,2-diphenyl-1-propanone was obtained (yield: 75 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-21 or B-39.

Comparative Example 40 Synthesis of 1,2-diphenyl-1-propanone from chlorobenzene and propiophenone Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-21 or B-39 were repeated except that 0.052 g (0.1 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-21 or 0.058 g (0.1 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-39 was replaced with 0.020 g (0.1 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 1,2-diphenyl-1-propanone formed.

Comparative Example 41 Synthesis of 1,2-diphenyl-1-propanone from bromobenzene and propiophenone Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-22 or B-40 were repeated except that 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-22 or 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-40 was replaced with 0.010 g (0.05 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 1.998 g of 1,2-diphenyl-1-propanone was obtained (yield: 95 mol % based on bromobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-22 or B-40.

Comparative Example 42 Synthesis of 1,2-diphenyl-1-propanone from bromobenzene and propiophenone Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-22 or B-40 were repeated except that 0.026 g (0.05 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-22 or 0.029 g (0.05 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-40 was replaced with 0.010 g (0.05 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 1,2-diphenyl-1-propanone formed.

Comparative Example 43 Synthesis of di-tert-butylphenyl malonate from chlorobenzene and di-tert-butyl malonate Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-23 or B-41 were repeated except that 0.031 g (0.06 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-23 or 0.035 g (0.06 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-41 was replaced with 0.012 g (0.06 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.746 g of di-tert-butylphenyl malonate was obtained (yield: 85 mol % based on chlorobenzene). The identification of the product was made by ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-23 or B-41.

Comparative Example 44 Synthesis of di-tert-butylphenyl malonate from chlorobenzene and di-tert-butyl malonate Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-23 or B-41 were repeated except that 0.031 g (0.06 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-23 or 0.035 g (0.06 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-41 was replaced with 0.012 g (0.06 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little di-tert-butylphenyl malonate formed.

Comparative Example 45 Synthesis of ethyl-2-phenylcyanoacetate from chlorobenzene and ethyl cyanoacetate Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-24 or B-42 were repeated except that 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-24 or 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-42 was replaced with 0.040 g (0.2 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 0.354 g of ethyl-2-phenylcyanoacetate was obtained (yield: 37 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-24 or B-42.

Comparative Example 46 Synthesis of ethyl-2-phenylcyanoacetate from chlorobenzene and ethyl cyanoacetate Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-24 or B-42 were repeated except that 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-24 or 0.116 g (0.2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-42 was replaced with 0.040 g (0.2 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little ethyl-2-phenylcyanoacetate formed.

Comparative Example 47 Synthesis of triphenylamine from chlorobenzene and diphenylamine Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-25 or B-43 were repeated except that 0.021 g (0.04 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-25 or 0.023 g (0.04 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-43 was replaced with 0.008 g (0.04 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 8.164 g of triphenylamine was obtained (yield: 83 mol % based on diphenylamine). The melting point was 125-126° C.

Comparative Example 48 Synthesis of triphenylamine from chlorobenzene and diphenylamine Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-25 or B-43 were repeated except that 0.021 g (0.04 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-25 or 0.023 g (0.04 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-43 was replaced with 0.008 g (0.04 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little triphenylamine formed.

Comparative Example 49 Synthesis of tert-butyl-2-methylphenyl ether from 2-chlorotoluene and sodium-tert-butoxide Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-26 or B-44 were repeated except that 0.784 g (1.5 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-26 or 0.868 g (1.5 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-44 was replaced with 0.303 g (1.5 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 7.712 g of tert-butyl-2-methylphenyl ether was obtained (yield: 94 mol % based on 2-chlorotoluene). The boiling point was 75° C./9 Torr.

Comparative Example 50 Synthesis of tert-butyl-2-methylphenyl ether from 2-chlorotoluene and sodium-tert-butoxide Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-26 or B-44 were repeated except that 0.784 g (1.5 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-26 or 0.868 g (1.5 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-44 was replaced with 0.303 g (1.5 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little tert-butyl-2-methylphenyl ether formed.

Comparative Example 51 Synthesis of 2-methoxy-4,2′-dimethylphenyl ether from 2-chlorotoluene and 2-methoxy-4-methylphenol Synthesis in which tri-tert-butylphosphine was handled in argon

The procedures in Example A-27 or B-45 were repeated except that 1.045 g (2 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-27 or 1.157 g (2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-45 was replaced with 0.405 g (2 mmol) of tri-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 6.958 g of 2-methoxy-4,2′-dimethylphenyl ether was obtained (yield: 76 mol % based on 2-chlorotoluene). The identification of the product was made by mass spectroscopy, ¹H-NMR and ¹³C-NMR, and the results were in agreement with those of Example A-27 or

Comparative Example 52 Synthesis of 2-methoxy-4,2′-dimethylphenyl ether from 2-chlorotoluene and 2-methoxy-4-methylphenol Synthesis in which tri-tert-butylphosphine was handled in air

The procedures in Example A-27 or B-45 were repeated except that 1.045 g (2 mmol) of tri-tert-butylphosphonium tetraphenylborate of Example A-27 or 1.157 g (2 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate of Example B-45 was replaced with 0.405 g (2 mmol) of tri-tert-butylphosphine. Tri-tert-butylphosphine generated white smoke while being handled in air. Little 2-methoxy-4,2′-dimethylphenyl ether formed.

Comparative Example 53 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which n-butyldicyclohexylphosphine was handled in argon

The procedures in Example B-48 were repeated except that 0.690 g (1.20 mmol) of n-butyldicyclohexylphosphonium tetraphenylborate of Example B-48 was replaced with 0.305 g (1.20 mmol) of n-butyldicyclohexylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 8.343 g of triphenylamine was obtained (yield: 85 mol % based on diphenylamine). The melting point was 125-126° C.

Comparative Example 54 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which n-butyldicyclohexylphosphine was handled in air

The procedures in Example B-48 were repeated except that 0.690 g (1.20 mmol) of n-butyldicyclohexylphosphonium tetraphenylborate of Example B-48 was replaced with 0.305 g (1.20 mmol) of n-butyldicyclohexylphosphine. Consequently, 2.943 g of triphenylamine was obtained (yield: 30 mol % based on diphenylamine). The melting point was 125-126° C. Handling n-butyldicyclohexylphosphine in air resulted in the lowered yield of triphenylamine.

Comparative Example 55 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which di-tert-butylphenylphosphine was handled in argon

The procedures in Example B-49 were repeated except that 0.065 g (0.12 mmol) of di-tert-butylphenylphosphonium tetraphenylborate of Example B-49 was replaced with 0.027 g (0.12 mmol) of di-tert-butylphenylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 9.020 g of triphenylamine was obtained (yield: 92 mol % based on diphenylamine). The melting point was 125-126° C.

Comparative Example 56 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which di-tert-butylphenylphosphine was handled in air

The procedures in Example B-49 were repeated except that 0.065 g (0.12 mmol) of di-tert-butylphenylphosphonium tetraphenylborate of Example B-49 was replaced with 0.027 g (0.12 mmol) of di-tert-butylphenylphosphine. Consequently, 6.869 g of triphenylamine was obtained (yield: 70 mol % based on diphenylamine). The melting point was 125-126° C. Handling di-tert-butylphenylphosphine in air resulted in the lowered yield of triphenylamine.

Comparative Example 57 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which 2-biphenylyl-di-tert-butylphosphine was handled in argon

The procedures in Example B-50 were repeated except that 0.074 g (0.12 mmol) of 2-biphenylyl-di-tert-butylphosphonium tetraphenylborate of Example B-SO was replaced with 0.036 g (0.12 mmol) of 2-biphenylyl-di-tert-butylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 8.535 g of triphenylamine was obtained (yield: 87 mol % based on diphenylamine). The melting point was 125-126° C.

Comparative Example 58 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which 2-biphenylyl-di-tert-butylphosphine was handled in air

The procedures in Example B-50 were repeated except that 0.074 g (0.12 mmol) of 2-biphenylyl-di-tert-butylphosphonium tetraphenylborate of Example B-50 was replaced with 0.036 g (0.12 mmol) of 2-biphenylyl-di-tert-butylphosphine. Consequently, 6.378 g of triphenylamine was obtained (yield: 65 mol % based on diphenylamine). The melting point was 125-126° C. Handling 2-biphenylyl-di-tert-butylphosphine in air resulted in the lowered yield of triphenylamine.

Comparative Example 59 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which di-tert-butyl-1-naphthylphosphine was handled in argon

The procedures in Example B-51 were repeated except that 0.071 g (0.12 mmol) of di-tert-butyl-1-naphthylphosphonium tetraphenylborate of Example B-51 was replaced with 0.033 g (0.12 mmol) of di-tert-butyl-1-naphthylphosphine, and except that the procedures were carried out in a glove box in which an argon atmosphere was strictly maintained. Consequently, 8.340 g of triphenylamine was obtained (yield: 85 mol % based on diphenylamine). The melting point was 125-126° C.

Comparative Example 60 Synthesis of triphenylamine from bromobenzene and diphenylamine Synthesis in which di-tert-butyl-1-naphthylphosphine was handled in air

The procedures in Example B-51 were repeated except that 0.071 g (0.12 mmol) of di-tert-butyl-1-naphthylphosphonium tetraphenylborate of Example B-51 was replaced with 0.033 g (0.12 mmol) of di-tert-butyl-1-naphthylphosphine. Consequently, 6.380 g of triphenylamine was obtained (yield: 65 mol % based on diphenylamine). The melting point was 125-126° C. Handling di-tert-butyl-1-naphthylphosphine in air resulted in the lowered yield of triphenylamine.

The results of Examples A-1 to A-4 confirmed that the trialkylphosphonium tetraphenylborates were produced more safely, by simpler reaction operations and in higher yields than by the conventional processes.

The results of Comparative Examples 3, 4, 7 to 16, and 19 to 52 confirmed that the trialkylphosphines could be used in combination with transition metals, salts thereof, oxides thereof or complexes thereof when the trialkylphosphines were handled in an inert gas, and that the trialkylphosphines were immediately oxidized in air and could not be used in combination with transition metals, salts thereof, oxides thereof or complexes thereof in air. The results of Examples A-5 to A-27 confirmed that the trialkylphosphonium tetraphenylborates could be used in combination with transition metals, salts thereof, oxides thereof or complexes thereof when the trialkylphosphonium tetraphenylborates were handled in air.

The results of Examples B-1 to B-17 and Examples B-46 to B-47 confirmed that the novel phosphonium borate compounds were produced more safely, by simpler reaction operations and in higher yields.

The results of Comparative Examples 1 to 60 confirmed that the alkylphosphines could be used in combination with transition metals, salts thereof, oxides thereof or complexes thereof when the alkylphosphines were handled in an inert gas, and that the alkylphosphines were immediately oxidized in air and could not be used in combination with transition metals, salts thereof, oxides thereof or complexes thereof in air. The results of Examples B-18 to B-45 and Examples B-48 to B-51 confirmed that the alkylphosphonium borate compounds could be used in combination with transition metals, salts thereof, oxides thereof or complexes thereof when the alkylphosphonium borate compounds were handled in air.

Claims

1. A process for producing a phosphonium borate compound, which comprises the following steps 1 and 2:

(step 1) reacting a phosphine with HCl to produce a phosphine hydrochloride, the phosphine being represented by Formula (II): (R1)(R2)(R3)P (II)

wherein R1 is a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R2 is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R3 is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R1, R2 and R3 may be the same or different from one another;

the phosphine hydrochloride being represented by Formula (III): (R1)(R2)(R3)PH.Cl (III)

wherein R1, R2 and R3 are as defined in Formula (II); and

(step 2) reacting the phosphine hydrochloride with a tetraarylborate compound represented by Formula (IV): M.BAr4 (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms;

the phosphonium borate compound being represented by Formula (I): (R1)(R2)(R3)PH.BAr4 (I)

wherein R1, R2 and R3 are as defined in Formula (II), and Ar is as defined in Formula (IV);

wherein step 1 is conducted in the absence of the tetraaryl borate compound used in step 2 and wherein the solution of the phosphine hydrochloride obtained in Step 1 and provided for step 2 is not subjected to concentration.

2. A process for producing a trialkylphosphonium tetraphenylborate according to claim 1, which comprises the following steps 1 and 2:

(step 1) reacting a trialkylphosphine with HCl to produce a trialkylphosphine hydrochloride, the trialkylphosphine being represented by Formula (II): (R1)(R2)(R3)P (II)

wherein R1, R2 and R3 are ethyl, n-butyl, tert-butyl or cyclohexyl groups, and are the same;

the trialkylphosphine hydrochloride being represented by Formula (III): (R1)(R2)(R3)PH.Cl (III)

wherein R1, R2 and R3 are as defined in Formula (II); and

(step 2) reacting the trialkylphosphine hydrochloride with a tetraphenylborate compound represented by Formula (IV): M.BAr4 (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is phenyl group;

the trialkylphosphonium tetraphenylborate being represented by Formula (I): (R1)(R2)(R3)PH.BAr4 (I)

wherein R1, R2 and R3 are as defined in Formula (II), and Ar is as defined in Formula (IV);

wherein step 1 is conducted in the absence of the tetraaryl borate compound used in step 2 and wherein the solution of the phosphine hydrochloride obtained in step 1 and provided for step 2 is not subjected to concentration.

3. A process for producing a novel phosphonium borate compound according to claim 1, which comprises the following steps 1 and 2:

(step 1) reacting a phosphine with HCl to produce a phosphine hydrochloride, the phosphine being represented by Formula (II): (R1)(R2)(R3)P (II)

wherein R1 is a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R2 is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R3 is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R1, R2 and R3 may be the same or different from one another;

the phosphine hydrochloride being represented by Formula (III): (R1)(R2)(R3)PH.Cl (III)

wherein R1, R2 and R3 are as defined in Formula (II); and

(step 2) reacting the phosphine hydrochloride with a tetraarylborate compound represented by Formula (IV): M.BAr4 (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms;

the phosphonium borate compound being represented by Formula (I): (R1)(R2)(R3)PH.BAr4 (I)

wherein R1, R2 and R3 are as defined in Formula (II), Ar is as defined in Formula (IV), R1, R2 and R3 cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time, and R1, R2 and R3 cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time;

wherein step 1 is conducted in the absence of the tetraaryl borate compound used in step 2 and wherein the solution of the phosphine hydrochloride obtained in step 1 and provided for step 2 is not subjected to concentration.

4. A process for producing a phosphonium borate compound, which comprises the following steps 1 and 2:

(step 1) reacting a phosphine with H2SO4 to produce a phosphine sulfate, the phosphine being represented by Formula (II): (R1)(R2)(R3)P (II)

wherein R1 is a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R2 is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R3 is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R1, R2 and R3 may be the same or different from one another;

the phosphine sulfate being represented by Formula (V): [(R1)(R2)(R3)PH](2-n).HnSO4 (V)

wherein R1, R2 and R3 are as defined in Formula (II), and n is an integer of 0 or 1; and

(step 2) reacting the phosphine sulfate with a tetraarylborate compound represented by Formula (IV): M.BAr4 (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms;

the phosphonium borate compound being represented by Formula (I): (R1)(R2)(R3)PH.BAr4 (I)

wherein R1, R2 and R3 are as defined in Formula (II), and Ar is as defined in Formula (IV);

wherein step 1 is conducted in the absence of the tetraaryl borate compound used in step 2 and wherein the solution of the phosphine sulfate obtained in step 1 and provided for step 2 is not subjected to concentration.

5. A process for producing a trialkylphosphonium tetraphenylborate according to claim 4, which comprises the following steps 1 and 2:

(step 1) reacting a trialkylphosphine with H2SO4 to produce a trialkylphosphine sulfate, the trialkylphosphine being represented by Formula (II): (R1)(R2)(R3)P (II)

wherein R1, R2 and R3 are ethyl, n-butyl, tert-butyl or cyclohexyl groups, and are the same;

the trialkylphosphine sulfate being represented by Formula (V): [(R1)(R2)(R3)PH](2-n).HnSO4 (V)

wherein R1, R2 and R3 are as defined in Formula (II), and n is an integer of 0 or 1; and

(step 2) reacting the trialkylphosphine sulfate with a tetraphenylborate compound represented by Formula (IV): M.BAr4 (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is phenyl group;

the trialkylphosphonium tetraphenylborate being represented by Formula (I): (R1)(R2)(R3)PH.BAr4 (I)

wherein R1, R2 and R3 are as defined in Formula (II), and Ar is as defined in Formula (IV);

wherein step 1 is conducted in the absence of the tetraaryl borate compound used in step 2 and wherein the solution of the phosphine sulfate obtained in step 1 and provided for step 2 is not subjected to concentration.

6. A process for producing a novel phosphonium borate compound according to claim 4, which comprises the following steps 1 and 2:

(step 1) reacting a phosphine with H2SO4 to produce a phosphine sulfate, the phosphine being represented by Formula (II): (R1)(R2)(R3)P (II)

wherein R1 is a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms;

R2 is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms;

R3 is a hydrogen atom, a primary alkyl group of 1 to 20 carbon atoms, a secondary alkyl group of 3 to 20 carbon atoms, a tertiary alkyl group of 4 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or an allyl group of 3 to 20 carbon atoms; and

R1, R2 and R3 may be the same or different from one another;

the phosphine sulfate being represented by Formula (V): [(R1)(R2)(R3)PH](2-n).HnSO4 (V)

wherein R1, R2 and R3 are as defined in Formula (II), and n is an integer of 0 or 1; and

(step 2) reacting the phosphine sulfate with a tetraarylborate compound represented by Formula (IV): M.BAr4 (IV)

wherein M is lithium, sodium, potassium, magnesium halide or calcium halide, and Ar is an aryl group of 6 to 20 carbon atoms;

the phosphonium borate compound being represented by Formula (I): (R1)(R2)(R3)PH.BAr4 (I)

wherein R1, R2 and R3 are as defined in Formula (II), Ar is as defined in Formula (IV), R1, R2 and R3 cannot be tert-butyl groups simultaneously and Ar cannot be phenyl group at the same time, and R1, R2 and R3 cannot be cyclohexyl groups simultaneously and Ar cannot be phenyl group at the same time;

wherein step 1 is conducted in the absence of the tetraaryl borate compound used in step 2 and wherein the solution of the phosphine sulfate obtained in step 1 and provided for step 2 is not subjected to concentration.